Di Livio was capped 40 times for Italy. He played for Italy at Euro 96, the 1998 FIFA World Cup, Euro 2000 (where Italy finished in 2nd place), and the 2002 FIFA World Cup. His first cap came on 6 September 1995 against Slovenia; his last on 18 June 2002 against South Korea. At Euro 1996, he set-up Pierluigi Casiraghi's first goal in the team's 2–1 win in the opening group match against Russia. For Italy, he was often used as a holding player to shut down games when the team was ahead, thus sealing the win.