Materazzi worked under Benitez at Inter in the first half of the 2010-11 campaign, and the former center back was not impressed with the coach's methods.
"He is not exactly my ideal coach. If I were in charge of a club, I would never entrust him with my team," Materazzi was quoted as saying by France Football.
He added, "What I did not like about him was the way he presented himself to the team. Great coaches like [Marcello] Lippi and [Jose] Mourinho use unwritten rules, but Benitez wanted to write 10 to 12 things down.
"It was like we were back to school or had to follow traffic rules."
Benitez replaced Roberto Di Matteo as Chelsea manager earlier this season