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Born in Barracas, a neighborhood of Buenos Aires, Di Stéfano was the son of Alfredo Di Stéfano, a first-generation Italian Argentine (his father Michele emigrated to Argentina from Nicolosi in the 19th century), and Eulalia Laulhé Gilmont, an Argentine woman of French and Irish descent with her relatives being from Swinford, County Mayo.

Following another heart attack on 5 July 2014, the 88-year-old Di Stéfano was moved to intensive care in the Gregorio Marañón hospital in Madrid, where he died on 7 July 2014.

On 8 July, his coffin was placed on public display at the Bernabéu Stadium. Real Madrid president Florentino Pérez and captain Iker Casillas were amongst those in attendance. Following his death Di Stéfano received tributes from many famous football personalities including Alex Ferguson, Johan Cruyff, Pelé, Cristiano Ronaldo, Diego Maradona and Bobby Charlton. During the 2014 FIFA World Cup semi-final between Argentina and the Netherlands on 9 July, Di Stéfano was honoured with one minute of silence, while the Argentine team also wore black ribbons in a matter of respect.

The Club Atlético River Plate from Argentina and Millonarios Fútbol Club from Colombia organized a friendly match in homage of their former player. The match was played on 16 July 2014, at the Millonarios' Estadio El Campín.

In 2013 an 86 year old Di Stéfano was in a relationship with his 36 year old personal secretary Gina González. He announced his plans to marry her in the same year, but passed before this happened.

In 2008 Di Stéfano was honoured by both UEFA and Real Madrid with a special Presidents award issued by FIFA at a ceremony in Madrid, where a statue was also unveiled. Then UEFA President Michel Platini called Di Stéfano "a great amongst the greats" while contemporaries Eusébio and Just Fontaine suggested that he was "the most complete footballer in the history of the game".

On 9 May 2006, the Alfredo di Stéfano Stadium was inaugurated at the City of Real Madrid, where Real Madrid usually train. Its inaugural match was between Real Madrid and Stade de Reims, a rematch of the European Cup final won by Real Madrid in 1956. Real Madrid won 6–1 with goals from Sergio Ramos, Antonio Cassano (2), Roberto Soldado (2), and José Manuel Jurado.

Following his signing by Real Madrid he was an integral part of one of the most successful teams of all time. He scored 216 league goals in 262 games for Real (then a club record, since surpassed by Raúl and Cristiano Ronaldo), striking up a successful partnership with Ferenc Puskás. Di Stéfano's 49 goals in 58 matches was the all-time highest tally in the European Cup. The record has since been surpassed by several players, with Real Madrid's Raúl the first in 2005.

A Spanish movie entitled Real, La Película (Real, The Movie), which recounted these events, was released on 25 August 2005. In a bizarre publicity stunt at the premiere, kidnapper Paul del Rio, now a famous artist, and Di Stéfano were brought together for the first time since the abduction, 42 years before.

On 24 December 2005, 79-year-old Di Stéfano suffered a heart attack.

In November 2003, to celebrate UEFA's Jubilee, he was selected as the Golden Player of Spain by the Royal Spanish Football Federation as their most outstanding player of the past 50 years. In 2004, he was named by Pelé in the FIFA 100 list of the world's greatest living players (in September 2009, he said Di Stéfano was the best Argentinian player "ever"). He was voted fourth, behind Pelé, Diego Maradona, and Johan Cruyff, in a vote organized by France Football magazine which consulted their former Ballon d'Or winners to elect the Football Player of the Century.

Di Stéfano resided in Spain until his death in 2014. On 5 November 2000 he was named Honorary President of Real Madrid.

After retirement, he moved into coaching. He guided the Argentine club Boca Juniors to league title, and won La Liga and the European Cup Winners' Cup with Valencia. He also returned to the club in 1986 to guide them back to La Liga by winning the Segunda Division after their relegation the season prior before his arrival. He also managed Sporting in the 1974/75 season and Real Madrid between 1982 and 1984. The 1982–83 was catastrophic for Real, they finished third in La Liga and were defeated finalists in the Supercopa de España, Copa de la Liga and Copa del Rey. Madrid were also beaten by Aberdeen, managed by Alex Ferguson, in the European Cup Winners' Cup final.

The Argentine veteran scored 9 goals in all competitions in his first season, putting an end to a strip of 15 consecutive seasons in which he scored in double figures (18 total). After 14 goals in 60 matches with Espanyol, he retired as a player at 40 in 1966, helping his team avoid relegation on both seasons. At the end of his career and despite what was previously stated, Bernabéu decided to throw a farewell match against Celtic in Madrid, to honour him for his services.

In the summer of 1964, Bernabéu proposes to 38 year-old Di Stéfano to join the technical staff of Real Madrid, and the Argentine declined the offer preferring to continue playing. That final against the Italian was Di Stéfano's the last game as the club decided not to renew his contract.

After the Champions Cup final loss in 1964 against Inter Milan, president Santiago Bernabéu and with Di Stéfano at the age of 38, offered him a place in the Real Madrid coaching staff instead of renewing the player contract. Di Stéfano refused Bernabéu's proposal and he moved to Real Espanyol.

The 1963-1964 season was the last of Di Stéfano at Real Madrid. At the beginning of the season, the team had a pre-season tour in Venezuela as the team participated in the 1963 Small Club World Cup against São Paulo and FC Porto. Di Stéfano played on the first match on 20 August but on 24 August 1963, the Argentine champion is kidnapped by the National Liberation Armed Forces of Venezuela in the Potomac hotel in Caracas, and was released by them three days later, unharmed. The incident cost the Los Blancos the trophy as without Di Stéfano they did not manage overcoming São Paulo in the final game. The Blancos clinched the fourth consecutive Liga and reached the final of the 1964 European Cup after defeating AC Milan in the quarterfinals (4-3). Real Madrid faced Helenio Herrera's Inter Milan in the final. Hours before the final, Di Stéfano explicitly criticized the tactics designed by Real Madrid coach Miguel Muñoz against Italian defender Giacinto Facchetti. The relationship between Muñoz, who had the support of President Bernabéu, and the Argentine player was already torn. And Inter Milan won the final by 3–1.

On the night of 24 August 1963, the Venezuelan revolutionary group Armed Forces of National Liberation (FALN), kidnapped Alfredo Di Stéfano at gunpoint from the Potomac Hotel in Caracas while his team, Real Madrid, were on a pre-season tour of South America. The kidnapping was codenamed "Julián Grimau", after the Spanish communist Julián Grimau García, executed by firing squad in Spain in April 1963 during Francisco Franco's dictatorship. Di Stéfano was released unharmed two days later close to the Spanish embassy without a ransom being paid, and Di Stéfano stressed that his kidnappers had not mistreated him. Di Stéfano played in a match against São Paulo the day after he was released and received a standing ovation.

In the autumn of 1962, the Blancos were knocked out of the European Cup, against Anderlecht. But, with Di Stéfano at the age of 37, Real won the 1963 title over Atletico Madrid, with Puskás finishing as top scorer once again.

In the 1961-1962 season Di Stéfano won the double for the first time, winning the Generalísimo Cup 15 years since the last time after beating Sevilla 2–1 with two goals from Puskás to overturn the initial red and white advantage. He finished 6th in the 1961 Ballon d'Or in December and . In the 1961-62 European season, Real reached the final of the tournament for the sixth time in its history, after eliminating Juventus and Standard Liegue. Real played against Eusébio's Benfica and though the Spaniards took the lead twice, in the second half of the game the Lusitanians won the title by 5–3, courtesy of Eusebio. Real lost its first European Cup final and for the first time Di Stéfano did not score in a final (the three goals were scored by Puskás). Nevertheless, he was among the best scorers of the competition for the second time in his career, with 7 goals.

In 1961, at the age of 36, Di Stéfano finally qualified for a World Cup, helping Spain qualify for the 1962 edition in Chile. A muscular injury just before the competition prevented him from playing in the finals, but Di Stéfano travelled with the squad anyway, picking the number 6 jersey as his preferred number 9 was taken by Francisco Gento. Spain boasted the likes of Jose Santamaria and Ferenc Puskás - both also naturalised citizens - but with Di Stéfano sidelined, they failed to make it out of the group stage, losing to Pele and Didi's Brazil in their final game and finishing at the bottom of their group. Di Stéfano retired from international football after the tournament.

The new season started with the inaugural Intercontinental Cup and the 0–0 draw in the first leg of the final against Peñarol in Montevideo on July 4. But in the second leg, Real beat the Uruguayans by 5–0 with Di Stéfano scoring one goal on 4 September 1960. On 13 December 1960, Di Stéfano came fourth on the 1960 Ballon d'Or voting, and for the first time, Real were knocked out of 1960-61 Champions Cup, against Barcelona (4-3) after a controversial return match. Real easily won the 1961 title with a great margin to runners-up Atletico Madrid, but lost again the final of the Generalísimo Cup, again to Rojiblancos (3-2). Di Stéfano finished the season with 21 goals, second scorer of the league behind Puskás who netted 28 goals.

After overcoming the rival citizens of Atlético Madrid after three games in semi-final, Real Madrid won its fourth consecutive Champions Cup by overtaking again Stade de Reims again with a score of 2–0. During the final, Enrique Mateos, the substitute of Puskás (the Hungarian feared retaliation and decided not to depart with the tam for the final in Stuttgart), took a penalty instead of Di Stéfano and missed it. But, in the beginning of the second half, Di Stéfano scored the second goal and Real Madrid was already a legend throughout the world, the most famous team that everyone wanted to watch. On 16 July, 1959, Real Madrid hosted Pele's Santos during their European tour. It was one of the most anticipated games of the tour, given of the reputation that Pele had started building. Di Stéfano's team would beat the Brazilians by 5–3. In December, France Football awarded Di Stéfano the 1959 Ballon d'Or, which he won ahead of team-mate Raymond Kopa (who had already returned to Stade de Reims in the summer of 1959) and Juventus's Welsh star John Charles. Puskás and Gento both finished in the top ten. That was when, during the 1959-1960 season, the Madrilenians signed the Brazilian midfielder Didi who was a World Cup winner, former teammate of Garrincha and Pele and the best player of the 1958 FIFA World Cup. Given that the style of play of the Brazilian was similar to Di Stéfano's, the Brazilian often clashed with the Argentine and there were rumours that he was the one to ask from the club's hierarchy his departure at the summer of 1960. But with Didi in the squad, the Blancos won the fifth consecutive Champions Cup, after eliminating Barcelona in the semifinals, Real Madrid played in the final of the Hampden Park in Glasgow in front of 135,000 spectators against Eintracht Frankfurt. Di Stéfano and Puskás scored three and four goals respectively, in a game considered to be among the finest in the history of football. Di Stéfano scored 8 goals in the 1960 competition, finishing second in the scorers' chart won by Puskás. In the 1960 season, Real finished equal with Barcelona on the table, but the Catalans were the ones to be awarded the title. Di Stéfano did not win the Pichichi award as Puskás was the topscorer of the league with 25 goals. And they lost Generalísimo Cup to Atletico Madrid by 3–1 home on 26 June 1960.

In the following season, Real Madrid is further strengthened with the arrival of Uruguayan José Santamaria in defense. Di Stéfano scored 19 goals and won the top scorer award, obtaining the 1958 title at the expense of Atletico Madrid. In the quarter-finals of the 1958 Champions Cup, Real Madrid faced Sevilla FC humiliating their opponents in the first leg in Madrid with an 8-0 where he scored four goals. On their return, in Seville, Di Stéfano was greeted by the insulting choruses of opposing fans and Real were held on 2–2. In the semifinals, Di Stèfano contributed to the success against Hungarian Vasas and the team reached the final against Juan Alberto Schiaffino's Milan. Real Madrid won the final with a 3–2 in comeback and the Argentinian all-around player finished the tournament as the top scorer with 10 goals.

But the season finished with the loss of the 1958 Generalísimo Cup after they lost 2-0 to Athletic Bilbao. As a result, Ferenc Puskás signed with Real Madrid in the summer of 1958 to strengthen the squad and Real Madrid would be blessed with one of the most lethal attacking pairs in the history of football. Nevertheless, Real finished second in the 1959 season behind Barça and Don Alfredo with 23 goals he was the best scorer in the league for the fifth and last time, the fourth in a row.

The Spanish team, with a forward line also boasting Barcelona and Real Madrid stars Laszlo Kubala, Luis Suárez and Francisco Gento, were favourites to qualify for the 1958 FIFA World Cup in Sweden, having been drawn into a qualification group with Scotland and minnows Switzerland. However, Spain began their campaign with a 2–2 draw against the Swiss and then lost to Scotland at Hampden Park 4–2. Spain won both of the reverse fixtures 4–1, but the damage had already been done: Scotland beat Switzerland in their final match and qualified at Spain's expense. Di Stéfano, who had played in all four games and scored two goals, missed out yet again.

He was awarded the Ballon d'Or for the European Footballer of the Year in 1957 and 1959. He moved to Espanyol in 1964 and played there until retiring at the age of 40.

Di Stéfano was widely loved in Spain, and having been banned from playing for Argentina, it made sense for Di Stéfano to play for Spain. FIFA initially refused to sanction this, but after Di Stéfano acquired Spanish citizenship in 1956, and amid pressure from the Spanish FA, the decision was eventually reversed. Di Stéfano consequently made his debut for Spain on 30 January 1957 in a friendly in Madrid, scoring a hat-trick in a 5–1 win to become one of a number of players born outside Spain to have appeared for their national team.

Di Stéfano scored in five consecutive European Cup finals for Real Madrid between 1956 and 1960, including a hat-trick in the last. Perhaps the highlight of his time with the club was their 7–3 victory over Eintracht Frankfurt in the 1960 European Cup Final at Hampden Park, a game many consider to be the finest exhibition of club football ever witnessed in Europe.

The second consecutive Spanish title allowed Real Madrid to be the first representative of Spain in the inaugural Champions Cup in its first edition in the 1955-1956 season. Di Stéfano made his Champions Cup debut against Servette in a 2–0 away win. In the league he was again the top scorer (24 goals), but despite that, Athletic Bilbao won the tournament ahead of Barça and Real. In the Champions Cup the team made their way eliminating the Swiss and later Partizan Belgrade, after a suffering a 3–0 defeat in Yugoslavia. With the guidance of Di Stéfano they had an easy 4–0 victory in Madrid in the first leg, in December 1956. Real Madrid team flew to Belgrade and, despite the snowstorm that had hit the city in the previous days, the president Bernabéu agreed for the match not to be postponed. Unlike the Spaniards, the Partizan players did not suffer on the terrain, took the lead and dominated the game. A penalty is awarded to Real Madrid, but Héctor Rial slipped when kicking and missed it. In the final minutes with the Serbians up by 3–0, Di Stéfano helped defending and Real qualified despite a clear defeat. The Blancos eliminated Milan in the semi-finals [64] and entered the final in Paris against Raymond Kopa and Just Fontaine's Stade de Reims. Real Madrid suffered in the first half, but Di Stéfano lifted his teammates to come back and win the trophy by 4–3. At the end of the year, on 18 December 1956, the Ballon s'Or was born and Di Stéfano missed the award for just 3 votes to Stanley Matthews.

In the summer of 1956, Real Madrid signed Raymond Kopa from the Stade de Reims. The French forward could not feature in the games due to the limit of foreigners in La Liga and had to wait for the Spanish naturalisation of Di Stèfano, who became a Spanish citizen in October 1956. The season started early with the participation of Real Madrid in the 1956 Small Club World Cup in Caracas, Venezuela as European champions. The Spaniards faced Vasco da Gama, AS Roma and FC Porto playing against players like World Cup winnerAlcides Ghiggia and Vavá. Real won the trophy with 3 wins and Di Stéfano finished as top scorer of the tournament with 4 goals (same as Vavá). As Real Madrid did not win the title in the previous season, president Santiago Bernabéu, who also served as the vice-president of the competition, came up with the idea that the Champions Cup winner had the right to register for the next edition to defend the victory even if it had lost the championship. Consequently, Real participated in the 1956-1957 season, eliminating Rapid Vienna, Nice and Manchester United in the semifinals and beating Fiorentina by 2–0 in the final, in Madrid. During the season, Real also asserted itself in the last edition of the Latin Cup , overcoming Benfica 1–0 in the final with a decisive goal by Di Stéfano and at the end of the year, he won the 1957 Ballon d'Or. From the twenty-third day of the 1956-1957 championship, Real Madrid started a series of consecutive victorious home results that ended only in 1966, at the twenty-fifth round of the Liga, after 121 matches. The Blancos attack was one of the best in history and boasted Di Stéfano, Héctor Rial, Francisco Gento and Kopa. Real won the 1957 championship and Di Stéfano was again the scorer of the Liga with 31 goals.

The following year, Real Madrid acquired Argentine Héctor Rial from the Nacional Montevideo, a signing recommended by Di Stéfano, for the attack of the Merengues. The club won another League in 1955 leaving Barcelona again in the second place of the table. Di Stéfano scored 25 goals, finishing behind only Juan Arza (28) among the scorers of the Spanish league. On 26 June 1955, the Spanish club won their first ever Latin Cup beating Raymond Kopa and Just Fontaine's Stade de Reims in the final, in Paris by 2–0.

Soon, after Millonarios' return to Colombia, the Barcelona directors visited Buenos Aires and agreed with River Plate, the last FIFA-affiliated team to have held the his card for the transfer of Di Stéfano in 1954 for the equivalent of 150 million Italian liras (according to other sources 200,000 dollars). That was when a head-to-head match between the two Spanish rivals for his purchase was born. In Christmas 1952, Di Stéfano still contracted with Millonarios, returned briefly to Buenos Aires, where he was even making plans to abandon football and start a business as Argentine league was still not professional.

Di Stéfano, nicknamed "Saeta rubia" ("Blond Arrow"), was a powerful, quick, skillful, and prolific forward, with great stamina, tactical versatility, creativity, and vision, who could also play almost anywhere on the pitch. He is currently the sixth highest scorer in the history of Spain's top division, and Real Madrid's third highest league goalscorer of all time, with 216 goals in 282 league matches between 1953 and 1964. He is Madrid's leading goalscorer in the history of El Clásico, alongside Cristiano Ronaldo.

FIFA expressed a favourable attitude towards Barcelona about the issue, sanctioning the contract of the player to the blaugrana. However the Spanish Football Association blocked the transfer. FIFA appointed Armando Muñoz Calero, former president of the Spanish Football Federation, linked to Francisco Franco, as mediator. Calero decided to let Real Madrid play the seasons 1953-1954 and in 1955-1956 and in Barcelona the years 1954-1955 and 1956–1957. The agreement was approved by the Football Association and their respective clubs. Although the Catalans agreed, the decision created various discontent among the Blaugrana members and the president who was forced to resign in September 1953.

A 27-year-old Di Stéfano arrived at Real Madrid on 22 September 1953, after seven months of inactivity, and made his debut with the white jersey in October 1953 in a clásico against champions Barcelona, won 5–0 with a hat trick by Di Stéfano. Real Madrid had an average team and had not won the title in 20 years. In his first months in Madrid, the Argentine champion did not adapt to European football, but imposed his own style, playing all around the field with speed and the ball low on the ground. At the first season with Real Madrid, Di Stéfano became the top scorer of the 1953–54 La Liga with 27 goals in 28 appearances, contributing significantly to the title victory: the Blancos managed to win the Spanish championship after two decades.

The 1952 league had the same outcome: Milionarios overtook Boca Juniors de Cali, won their third title and Di Stéfano was once again top-scorer with 19 goals. In October 1952, Di Stéfano also led Millonarios to the final of Copa Colombia after beating Deportivo Cúcuta by 2–1. The final would be played in May 1953, but with Di Stéfano already in Argentina.

In March 1952, Real Madrid organized a friendly tournament in the Spanish capital, at its newly constructed home ground, River Plate was invited to participate in Real Madrid's 50th-anniversary tournament. The tournament was called Bodas de Oro, but once Real Madrid's Santiago Bernabeu heard about the new powerhouse in South America, Millonarios cancelled the invitation to River Plate and invited the Colombians as the representative of South America. The Colombians participated in the tournament and won it, after drawing 2–2 with Swedish champions IFK Norrkoping and overcoming the Los Blancos who were managed by Argentine legend Hector Scarone by 4–2 with a brace from Saeta Rubia under the presence of President Santiago Bernabéu, who arrived to the stadium to observe Adolfo Pedernera. Instead, Bernabéu asked Millonarios about Di Stéfano and a deal was struck between him and Millonarios owner Alfonso Senor Quevedo, both sympathetic to the conservative regimes of the time in Spain and Colombia. Millonarios would start a global tour and spearheaded by Di Stéfano, they would beat Hungary and world champions Uruguay.

In October 1951 DIMAYOR had agreed the Pacto de Lima with the FIFA, with the requirement that the foreign players would return to their countries after October 1954. He totally scored 267 goals in 292 goals for Milionarios and is considered still as one of the best footballers the history of the Colombian League.

Di Stéfano's six games during that tournament would prove to be his only appearances for Argentina. Player strikes, and a dispute with the Brazilian Football Confederation, forced Argentina to withdraw from qualifying for the 1950 FIFA World Cup in Brazil, as well as the 1949 and 1953 South American Championships. By the time qualifying began for the 1954 FIFA World Cup, FIFA had banned Di Stéfano from making any further appearances for Argentina, on account of his appearances for the Colombia XI two years earlier - though Argentina once again pulled out of qualifying.

Di Stéfano married Sara Freites in 1950, they had six children: Alfredo, Ignacio, Sofia, Silvana, Helena and Nanette. Sara died in 2005.

Upon his return to River Plate, Di Stéfano became integral part of La Máquina taking on the role of the departing Adolfo Pedernera who had signed for Club Atlético Atlanta. Carlos Peucelle initially put Di Stéfano on the flank, a position in which Di Stéfano struggled to play; in a game against Atlanta of Pedernera, Peucelle decided to place him as a center forward and River eventually won by 6–1. Soon, Di Stéfano imposed himself as the center forward and his teammates adapted to his game. This is when he obtained the nickname of Saeta Rubia, coined by journalist Roberto Neuberger. Though he had to leave the team for some time due to the compulsory conscription, Di Stéfano contributed significantly to the victory of the 1947 Argentine Primera División, and became the top scorer of the league with 27 goals. The victory in the league gave River Plate the right to represent Argentina in the Copa Aldao against the champions of Uruguay Nacional Montevideo who featured great player like goalkeeper Anibal Paz and Walter Taibo in a two-nation club competition that tracked origins to 1913 and for many it was considered as the precursor to the Copa Libertadores. On November 1947, River beat Nacional 4–3 with Di Stéfano scoring one goal in Montevideo and four days later, Di Stéfano celebrated his first international club trophy with a 3–1 victory in Buenos Aires. In February 1948, champions River Plate participated in the inaugural South American Championship of Champions in Santiago facing the other South American champions finishing second behind Vasco da Gama and Di Stéfano scored 4 goals in 6 games. During the Argentinian championship of 1948, the Football Association suspended the tournament for a short time due to the protests of the players led by Adolfo Pedernera and Alfredo Di Stéfano and materialised with a player's strike in a bid to gain a professional footballer's status and rights. Despite that upheaval Di Stéfano scored 13 goals in 23 games and River Plate finished third. The strike last for 8 months until 1949 and it eventually meant the departure of the best Argentine footballers towards other championships, in particular towards that Colombian, which was one of the lucrative in the world at the time. In one of his last games in Argentina, on 31 July 1949, Di Stéfano played in the role of goalkeeper, replacing the owner Amadeo Carrizo for twenty minutes and keeping the clean sheet in a derby won against Boca Juniors.

After the Superga air disaster, in May 1949, a friendly match between River Plate and Grande Torino was played and Di Stéfano was promised to the Granata. However the Argentine forward was soon after contacted by Adolfo Pedernera who had already agreed terms with the Colombian Bogota-based club of Millonarios F.C.. On 9 August 1949, after another one of his teammates, Néstor Rossi signed for the Colombian club without the president of River Plate receiving any compensation for the transfer of the players as the Colombian FA was still not affiliated with FIFA, Di Stéfano signed for the Colombians. Millonarios who anyway could not afford not to pay the transfer fees, offered him a salary clearly higher than that received at River Plate, and the Argentine forward started a new chapter in his career in Colombia, in period called El Dorado. Many international stars like the Hungarians Béla Sárosi, László Szőke, Lithuanian Vytautas Kriščiūnas, the Argentines René Pontoni, Héctor Rial, English Charlie Mitten from Manchester United for 5.000 pounds a year, Neil Franklin from Stoke City, French-Hungarian Ferenc Nyers, Italian Luigi Di Franco, the Brazilian legend Heleno de Freitas and others had joined the league after legendary Perdenera first signed. The Colombian League became at the time the best in the world and with the highest salaries.

The Colombian league had turned professional in 1948 started the El Dorado period on 25 April 1949. Di Stéfano, Perdenera and Nestor Rossi who joined Millonarios in the summer formed the famous trio called the Ballet Azul and helped them win their first title ever beating Deportivo Cali in the 1949 final, with Di Stéfano scoring 16 goals in 14 games. Di Stéfano scored 23 goals in 29 games the following 1950 season, but Millonarios finished 2 points behind eventual champions Deportes Caldas. Di Stéfano, who kept in excellent condition, excelled during his games and led Millonarios to the other second title in 1951 leaving runners-up Boca Juniors de Cali by 11 points behind on the final table and scoring 32 goals in 34 games, more than any other player in the league. Millonarios would go on to lose the Copa Colombia of 1951 (played in 1952) to Boca Juniors de Cali.

After moving to Bogota in 1949, during a break in the Colombian League in 1951, friendly matches were organised under the name of combined XI of the Colombian league. Di Stéfano - without ever holding a Colombian passport - made four appearances for the Colombian XI team, which did not appear in the official records of FIFA.

Di Stéfano made his international debut on 4 December 1947, in a match against Bolivia at the Estadio George Capwell in Ecuador, during the 1947 South American Championship. He scored his first international goal in that same match, helping Argentina to a 7–0 win. Di Stéfano scored five more goals during the championship - including his first hat-trick against Colombia - as Argentina successfully defended the title they had won the previous year on home soil.

During the only match Di Stéfano played in the previous season, the president of Huracán was impressed by his potential; Di Stéfano agreed, as he realised his chances of making the first team for River Plate were limited. Huracán and Argentina legend Herminio Masantonio had just retired and the club needed a replacement forward. Former Argentine striker and World Cup top scorer Guillermo Stábile, the Huracán and Argentine national team coach at the time, gave Di Stéfano his first real opportunities in the 1946 season. He scored the first two goals of his career in a 3–1 victory against Estudiantes (LP). He later scored against his former team River Plate, netting the fastest goal in the history of the Argentine championship, after about ten seconds of play. He would score 10 goals in 25 appearances for Huracan, teaming up perfectly with Norberto Méndez who would later become the all-time top scorer in Copa América. Huracán tried to sign Di Stéfano permanently at the end of a successful eighth-placed season, but could not afford the 90.000 pesos River Plate asked for the transfer.

In 1944 his father wrote a letter of recommendations to River Plate and the club sent a reply telegram to invite him to an audition with the youth team. Di Stéfano impressed on the trial and joined the squad of the second team of River Plate, the club his family supported. The next year he became part of the first team which was called La Máquina due to their unprecedented success and it was consisted of players like the legendary Pedernera, Labruna Muñoz, and Loustau. One of the main stars of the team Moreno had just left for the Mexican Real Club España and it seemed like a good opportunity for the young Di Stéfano to fight for a place in the first squad. Di Stéfano, whose idol was Paraguayan Arsenio Erico , the striker of Independiente, learned from the qualities of the big stars especially Pedernera. His coach, and first mentor Carlos Peucelle, taught him how to play the ball low and soon he made his first team debut in 1945, at the age of 19: on July 15 of that year he debuted against Huracán in 2–1 defeat for the twelfth day of the 1945 Argentine championship. That was the only game Di Stéfano played in that year, but at the end of the season he won his first title as River Plater won the championship, leaving Boca Juniors four points behind.

He began his career at Argentina's River Plate aged 17, in 1943. For the 1946 season he was loaned to Club Atlético Huracán, but he returned to River in 1947. Due to a footballers' strike in Argentina in 1949, Di Stéfano went to play for Millonarios of Bogotá in the Colombian league. He won six league titles during the first 12 years of his career in Argentina and Colombia.

Alfredo Stéfano Di Stéfano Laulhé (Spanish pronunciation: [alˈfɾeðo ði esˈtefano] ; 4 July 1926 – 7 July 2014) was an Argentine professional footballer and coach. He is regarded as one of the best footballers of all time, and is best known for his achievements with Real Madrid, where he was instrumental in the club's domination of the European Cup and La Liga during the 1950s. Along with Francisco Gento and José María Zárraga, he was one of only three players to play a part in all five victories, scoring goals in each of the five finals. Di Stéfano played international football mostly for Spain after moving to Madrid, but he also played for Argentina and Colombia.

Di Stéfano's father, who a former defender of the River Plate, but prematurely retired in 1912 due to knee injury, introduced young Alfredo to football. Di Stéfano grew up playing street football, in oratories and in neighbourhood teams such as the Barracas "Unidos y Venceremos", and the Imán of the Flores district. People already had noticed his talent. But, in 1940 his family moves to the countryside and Di Stéfano started working with his father and playing football with his brother Tulio in the Club Social y Deportivo Unión Progresista until 1943, when the family returned to Buenos Aires.