The Portuguese won the Supercoppa Italiana, the Coppa Italia, two Serie A titles and the UEFA Champions League during his two-year spell with the Italian side.
He quit the club in May 2010 to join Real Madrid, with former Liverpool boss Benitez appointed as his replacement the following month.
However, he endured a difficult time at the Giuseppe Meazza and despite winning the Club World Cup he was sacked in December, just six months after his appointment.
Materazzi, who left Inter at the end of the 2010/11 season, looks back fondly on his time at the club with Mourinho in charge but is scathing of his successor Benitez.
"Mourinho was number one. His secret was to make the players feel involved in the project," he told Sport Mediaset.
"In Madrid [during the 2010 Champions League final], he told me that he was leaving. I said to him: 'Damn you for leaving me with Benitez.'
"I did not get on well with Benitez. I had the front pages from newspapers showing the most important moments of my career, Inter with Mou [Jose Mourinho], Italy with [Marcelo] Lippi and Benitez made me take them down.
"He thought he knew everything, but he was afraid of his own shadow."