Di Biagio continued to be a key player for Italy under Dino Zoff, and he went on to represent Italy at Euro 2000, starting alongside Albertini in midfield, and winning a runners-up medal as Italy lost 2–1 to France in the final on a golden goal. Di Biagio had another successful tournament for Italy, and he scored Italy's first goal against Sweden, heading in a Del Piero corner, in Italy's final group match, which ended in a 2–1 win, and which allowed Italy to top their group and progress to the quarter-finals. In the victorious semi-final penalty shootout against co-hosts the Netherlands, he took Italy's first penalty, and was able to convert it successfully on this occasion. It was the first penalty he had taken after the infamous miss which struck the crossbar during the 1998 World Cup, which immediately eliminated Italy from the competition.