He scored 216 league goals in 282 games for Real (then a club record, since surpassed by Raúl, Cristiano Ronaldo and Karim Benzema), striking up a successful partnership with Ferenc Puskás.

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 on the first squad.

Former Argentine striker and World Cup top scorer Guillermo Stábile, the Huracán and Argentina national team coach at the time, gave Di Stéfano his first real opportunities in the 1946 season.

Upon his return to River Plate, Di Stéfano became an integral part of La Máquina, taking on the role of the departing Adolfo Pedernera who had signed for Club Atlético Atlanta.

Though he had to leave the team for some time due to compulsory conscription, Di Stéfano contributed significantly to winning the 1947 Argentine Primera División, becoming the top scorer of the league with 27 goals.

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 a few minutes and keeping the clean sheet in a derby won against Boca Juniors.

Millonarios, who could not afford to pay the transfer fees anyhow, offered him a salary clearly higher than that 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, the Argentines René Pontoni, Héctor Rial, Englishman 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 Heleno de Freitas and others had joined the league after Pedernera first signed.

The Colombians participated in the tournament and won it, after drawing 2–2 with Swedish champions Norrköping and overcoming Los Blancos, who were managed by Uruguayan legend Hector Scarone, by a 4–2 margin with a brace from Saeta Rubia in the presence of President Santiago Bernabéu, who arrived to the stadium to observe Adolfo Pedernera.

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 Di Stéfano's rights, for his transfer in 1954 for the equivalent of 150 million Italian lira (according to other sources 200,000 dollars).

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 the Argentine league was still not professional.

Highlights of his first season included two match-winning performances against city rivals Atlético Madrid, with a hat-trick in a 5–0 away win in November 1953, and scoring the two goals in a 5–0 home comeback in February 1954.

Despite the surprise sacking of manager Enrique Fernández halfway through the season, the club won another league title in 1955 with José Villalonga, leaving Barcelona again in the second place of the table.

At the end of the year, on 18 December 1956, the first Ballon d'Or was awarded, and Di Stéfano missed on winning it by just three votes to Stanley Matthews of English club Blackpool.

In December, France Football awarded Di Stéfano the 1959 Ballon d'Or, which he won ahead of teammate Raymond Kopa (who had already returned to Stade de Reims in the summer of 1959) and Juventus's Welsh star John Charles.

On 13 December 1960, Di Stéfano came fourth in the Ballon d'Or voting, and for the first time in history, Real Madrid were knocked out of the European Cup, losing 3–4 on aggregate against Barcelona after a controversial second leg.

In the showpiece, Madrid played against defending champions Benfica and though the Spaniards took the lead twice, in the second half of the game the Lusitanians cruised to successfully retaining their title with a thrilling 5–3 victory, courtesy of Eusébio.

[8][23] The season, however, went on to be quite successful, with the Blancos clinching their fourth consecutive league title and returning to the European Cup final, having defeated AC Milan in the quarter-finals 4–3 on aggregate along the way.

Hours before the final, Di Stéfano explicitly criticized the tactics designed by Real Madrid head coach Miguel Muñoz against Italian defender Giacinto Facchetti.

The relationship between Di Stéfano and Muñoz, who had the support of President Bernabéu, had been problematic for over a year and reached its climax in the final, which Inter won 3–1, a match in which both came to accuse each other of the defeat.

[26] After the Champions Cup final loss in 1964 against Inter Milan, president Santiago Bernabéu offered Di Stéfano a place on the Real Madrid coaching staff instead of renewing the player's contract.

[24] In late July, Di Stéfano even went to Milan accompanied by Luis Carniglia to meet the club's leaders and issue a counteroffer to Espanyol's proposal, but the Italians were not willing to undertake his signing at any price and they already had the three foreign players allowed per squad.

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.

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.

At the same time the División Mayor del Fútbol Profesional Colombiano league had split from the Colombian football federation resulting in an international ban for the clubs and players alike.

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.

[47] Regarded as a very strong player, Di Stéfano was a powerful, quick, skillful, and prolific goalscorer, with great stamina, tactical versatility, creativity, and vision, who could play almost anywhere on the pitch.

[57] Following his death Di Stéfano received tributes from many famous football personalities including Alex Ferguson, Pelé, Cristiano Ronaldo, Diego Maradona, and Bobby Charlton.

[58] 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.

[62] In 2013, Di Stéfano's children won custody of him and his assets in order to prevent his planned wedding to Gina González, his Costa Rican secretary who was 50 years younger than him.