Sardinian-born Materazzi is best remember as one of the most representative players for U.S. Lecce, where he spent seven years and played 228 Serie C matches. He also played for Tempio, Reggina and Bari.
Materazzi started his coaching career in 1979, for Tuscan Serie C2 team Cerretese. He first coached Serie A team, Pisa SC, in 1987/1988, leading the side to a 13th place finish. He then coached Lazio for two seasons, before to move to Serie B side Messina in 1990. His longest period as football coach started in 1992 in Bari, where he already played in his past career and coached, but at the youth level. He stayed four years in Bari, two of them in Serie A. He then coached a number of minor Serie A and Serie B teams, such as Padova, Brescia, Piacenza, before being signed by Sporting Clube de Portugal in July 1999. However his experience lasted just a few months, as Materazzi was fired on September 1999 after a UEFA Cup loss to Viking F.K.. On early November he was called by Venezia chairman Maurizio Zamparini to replace Luciano Spalletti at the helm of that Serie A team, but was fired just 27 days later, and notably replaced by Spalletti. His last club experience came in January 2001, as Materazzi was appointed to coach Cagliari of Serie A.
On February 26, 2007, Materazzi was appointed head coach of Serie B club Bari, replacing Rolando Maran. He led his club to a quiet escape from relegation, and was confirmed for the 2007-08 season. He resigned from his post on December 27, 2007, shortly after being defeated 4–0 at home by Lecce in the Apulian derby.
On 30 December 2008 Materazzi signed a contract to become the head coach of Olympiakos Volos, after just two months, Materazzi has decided to quit Volos on 6 March 2009. The Italian trainer has decided to resign because he has not reached the targets that he had fixed.