Materazzi was signed by Inter Milan in July 2001 for €10 million. He took squad number 23 and made his competitive debut for the club on 26 August in the opening championship match against Perugia. Materazzi's first goal for Inter came only in his second appearance, netting inside 10 minutes in a 2–2 draw at Parma. He also played eight time in the season's UEFA Cup, with his competition debut coming on 20 September in the 3–0 win versus Romania's Brașov.