He represented several Italian clubs in Serie A throughout his career, coming to prominence with Juventus, where he won several domestic and international titles.

Having failed to make an appearance in his only season for the club, Di Livio played for Reggiana (1985–86), Nocerina (1986–87), Perugia (1987–89), Padova (1989–93), Juventus (1993–99) and Fiorentina (1999–2005).

His tireless running and quality crossing made him an important element in the dominant Juventus starting lineup from 1993 to 1999, during one of the most successful periods in the club's history.

[6] A quick, experienced, energetic, combative, reliable, and tactically versatile player, Di Livio was usually deployed on the right wing, although he was capable of playing on either flank, as either a wide midfielder, or as a full-back or wing-back, courtesy of his ability with either foot; he was also capable of playing in the centre, as a box-to-box or defensive midfielder, or even in defence.

Although he was not the most naturally talented or skilled footballer from a technical standpoint, he was a highly consistent, intelligent, and disciplined player, who was known for his pace, stamina, work-rate, and strength, despite his diminutive stature.