The pair share a frosty relationship which dates back to Benitez's brief stint in charge of Inter back in 2010.
World Cup winner Materazzi has now reignited that bitterness by describing Benitez as a "weak person", while also heavily criticising his management style.
"[Rafael Benitez] is not my ideal coach. If I was a club president, I'd never employ him," he told France Football. "A great boss like Lippi or Mourinho knows how to get their demands across to a dressing room. Whereas Benitez, he wanted to put them all in writing, ten or twelve rules - like the Highway Code, or being at school.
"At Inter's training centre, there were photos on the wall of all the most successful past coaches, from Herrera to Mancini and Mourinho.
"Benitez had the ones of Jose taken down. With that gesture, he showed his character - that of a weak person."
Materazzi called time on his career in 2011 following 10 years at the San Siro.