In 2010, Di María moved to Spanish club Real Madrid in a transfer worth €25 million, where he won a 2011–12 La Liga title and the 2013–14 UEFA Champions League.

Di María debuted for Argentina internationally in 2007, playing for the under-20 team; with the side, he won the 2007 FIFA U-20 World Cup, held in Canada.

Due to the low income his family earned, purchasing football boots and keeping up with Di María's hobby was difficult for his parents.

[7] Di María made his professional debut on 14 December 2005 in Rosario's final fixture of the Apertura, a 2–2 draw away to Independiente, by replacing Emiliano Vecchio.

[11] He was also approached by English club Arsenal, a move that fell through due to the United Kingdom's strict rules on issuing work permits to players from outside the European Union.

On 22 October, in the Europa League group stage match against Everton, he provided a hat-trick of assists for the first time in his career, in a 5–0 thrashing at the Estádio da Luz, marking the biggest loss of an English side in a European competition.

In the second leg of the Champions League round of 16 against Lyon, he scored the third and final goal in a 3–0 win to send Real Madrid through to the quarter-finals for the first time in seven years.

[34] During the start of the 2011–12 season, Di María endured a tough series of matches as he struggled to adapt to the pace of the league following the summer break.

From October 2011, Di María was being picked by Madrid head coach José Mourinho ahead of Kaká and Mesut Özil, a sign of his improving form.

[43] In the 2014 UEFA Champions League Final against Atlético Madrid on 24 May 2014, Di María dribbled past two players before producing a save from goalkeeper Thibaut Courtois.

Di María's teammate Gareth Bale, was there to head the rebound into the net in the 110th minute, giving Real Madrid a 2–1 lead over Atlético in an eventual 4–1 win.

[46] A week later, in the first leg of the Supercopa de España, he played the final 15 minutes of a 1–1 home draw against Atlético Madrid in place of Luka Modrić.

[49][50][51] He inherited the number 7 shirt at United, which was previously worn by club legends such as George Best, Bryan Robson, Eric Cantona, David Beckham and Cristiano Ronaldo.

[58] On 2 October, Di María won Manchester United's Player of the Month award for September after recording two goals and two assists in his first four matches for the club.

[60] Di María continued his run of fine form on 5 October by scoring a goal and providing an assist for Radamel Falcao to help United defeat Everton 2–1.

[64] Di María was sent off on 9 March as United lost 2–1 at home against Arsenal in the FA Cup sixth round, being booked for diving and for grabbing the shirt of referee Michael Oliver, but earlier set up the equaliser by Wayne Rooney.

[68] On 2 August, it was reported Di María would undergo a medical ahead of a move to Paris Saint-Germain;[69] and four days later, Manchester United confirmed he had been sold to the French champions for an undisclosed fee, believed to be around £44 million, signing a four-year contract.

[70][71][72][73] Di María made his Ligue 1 debut on 30 August away to Monaco as a 66th-minute substitute for Lucas, and assisted Ezequiel Lavezzi for the final goal of a 3–0 win at the Stade Louis II.

[74] On 15 September, Di María scored his first goal for PSG on his UEFA Champions League debut for the club, a 2–0 win over Malmö FF at the Parc des Princes.

On 14 February 2017, Di María scored a brace as PSG defeated Barcelona 4–0 in the first leg of 2016–17 UEFA Champions League round of 16 at the Parc des Princes.

[82] On the first leg of his side's Champions league round of 16 tie against his former club Manchester United in the 2018–19 season, Di María sustained a serious injury following a tackle from Ashley Young; however, he refused to be substituted, and in the final moments of the game, he assisted Kylian Mbappé's goal for a 2–0 win at Old Trafford.

[85] On 18 August 2020, Di María scored a goal and recorded two assists in PSG's 3–0 Champions League semi-final victory over RB Leipzig;[86] the club went on to play against Bayern Munich in the final, but lost the match 1–0.

[87] On 23 September 2020, Di María was handed a four-match suspension for a spitting incident with Álvaro González during Le Classique 10 days earlier.

[109][110] On 9 August, Di María made his second debut at Benfica, scoring the opening goal of a 2–0 victory over Porto in the Supertaça Cândido de Oliveira, winning his first trophy back with the club.

[121] Following the World Cup, on 11 August 2010 Di María scored the first-ever international goal at Dublin's new Aviva Stadium in a friendly against the Republic of Ireland as Argentina won 1–0.

[123] Di María made 12 appearances during the 2014 FIFA World Cup qualification campaign[119] and was included in the Argentina national team for the tournament finals.

[131] A week later, in their opening match of the tournament against Paraguay in La Serena, Di María won a penalty which Messi scored in a 2–2 draw.

[136] He missed the rest of the tournament due to injury[137] as Argentina reached the Copa América final for the second consecutive time, once again losing out to Chile on penalties, following a 0–0 draw.

[152] Di María is a quick, strong, tricky and talented winger who is also capable of playing as a more central attacking midfielder or on either side of the pitch, although he is predominantly a left-footed player.

He is also gifted with excellent vision, set-piece delivery, passing, and crossing ability, which allow him to function effectively as a playmaker and as an assist provider, although he is also capable of scoring goals himself, and is an accurate free kick taker.