Despite huge success on the club level, he has been somewhat disappointing playing for Italy, although he is currently the team's fourth all-time leading scorer. His tournament debut was Euro 96, but made his only appearance in the first half of a match against Russia before being substituted at halftime. Del Piero competed with fan favorite Baggio for a spot on the 1998 FIFA World Cup final roster while struggling to recover from injury suffered during the 1998 Champions League final with Juventus. He also missed two chances in Italy's 2-1 loss to France in the Euro 2000 final.
He returned to the international scene in the 2002 FIFA World Cup on the back of an impressive season in Serie A, in which he led Juventus to the Scudetto. Del Piero scored the decisive goal against Hungary, which sealed the Azzurri's qualification for the finals. He instantly scored against Mexico after coming on as a substitute to send Italy through to the second round, where they were eliminated. After Euro 2004, Marcello Lippi was replaced by Fabio Capello as Juventus coach. Capello was not convinced of Del Piero's abilities and frequently benched him in favor of new signing Zlatan Ibrahimović, but Del Piero still managed to score 14 goals as Juventus won their 28th league title.
Del Piero began the 2006 World Cup on the bench, appearing in two out of three group stage matches, and made his first start of the competition in a 1-0 round-of-16 win over Australia on June 26. On July 4, Del Piero entered as a substitute near the end of regulation and scored Italy's second goal in a 2-0 semifinal win over host Germany. The final whistle blew 8 seconds after he scored. In the final against France, which ended 1-1 after extra time, Del Piero scored a penalty in the shootout as Italy won the tournament for the fourth time. He admitted afterwards that winning the World Cup was his childhood dream.
As of 2006, Del Piero has captained Italy five times (including the world cup in 2006) . He also regularly wore the number 10, but later gave it to Francesco Totti and switched to the number 7, as it was the first number he wore at the start of his career. Even though the number 10 was vacated after Totti retired from the national team in July 2007, Del Piero denied any interest in taking back the number, saying he was satisfied with the number 7.
Del Piero was called up to Italy's squad for the UEFA Euro 2008 Championship in Austria and Switzerland. Italy qualified through the group stage in second-place behind Holland, eliminating Romania and France. In the quarter-final against Spain, Del Piero made a substitute appearance during extra-time, and with the game ending in a 0-0 draw, it was decided by a penalty shootout. Spain won 4-2.