In June 2021, he was included in Italy's preliminary squad for UEFA Euro 2020 by manager Roberto Mancini, but he was initially left out of the final 26-man squad for the tournament. However, following an injury to Stefano Sensi, Pessina was called up to the tournament in his place. He made his first appearance in the tournament as a late substitute in Italy's group match against Switzerland on 16 June, a 3–0 win for Italy. He then started in the match against Wales on 20 June, scoring the only goal of the match in the team's 1–0 victory in Rome; the result allowed them to top their group. On 26 June, after coming off the bench for Nicolò Barella, Pessina scored the match–winning goal in a 2–1 win in extra-time over Austria in the round of 16, which allowed Italy to progress to the quarter-finals. On 11 July, Pessina won the European Championship with Italy following a 3–2 penalty shoot-out victory over England at Wembley Stadium in the final, after a 1–1 draw in extra-time.