In the 2019–20 UEFA Champions League group stage, Di María scored a brace in a 3–0 win over his former club Real Madrid on 18 September 2019. 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; the club went on to play against Bayern Munich in the final, but lost the match 1–0.