Materazzi began his footballing career with the Lazio and then the Messina Peloro youth teams from 1990 to 1991. He spent his early career in the lower divisions of Italian football, with amateur side Tor di Quinto (1991–92), Serie C2 team Marsala (1993–94), and Serie C1 Trapani (1994–95), where he narrowly missed a historic promotion to Serie B after losing a promotion playoff to Gualdo. Serie B squad Perugia Calcio signed Materazzi for the first time in 1995, but he spent a part of the 1996–97 season in Serie C with Carpi.