In 1999, he moved to Fiorentina, where he captained the team to win the Coppa Italia during the 2000–01 season. In 2002, when AC Fiorentina went bankrupt and was reborn as "Florentia Viola" in Serie C2, Di Livio showed his dedication by being the only player to stay with the team, as he played through the depths of Italian football on the climb back to Serie A in 2004, finally retiring after the conclusion of the 2004–05 Serie A season.