Benitez has not been on good terms with the World Cup-winning Italian defender since he took charge of the treble-winning Inter side in the summer of 2010, succeeding Jose Mourinho.
The now Chelsea manager left the Milan-based club after a disappointing set of results, and has hit back at Materazzi after the defender criticised his methods.
In an interview with France Football this week, Materazzi had said: "He is not my ideal coach. If I was a club president, I'd never employ him.
"A great boss like (Marcelo) Lippi or Mourinho knows how to get their demands across to a dressing room whereas Benitez, he wanted to put them all in writing - 10 or 12 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 (Helenio) Herrera to (Roberto) Mancini and Mourinho. Benitez had the ones of Jose taken down. With that gesture, he showed his character: that of a weak person."
Materazzi had also told Sport Mediaset back in November: "Mourinho was number one. His secret was to make the players feel involved in the project.
“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.'"
Benitez used a press conference to undermine Materazzi’s comments, dismissing the examples cited by the defender.
"He's lying," Benitez said. "Marco Materazzi's lying. He's lying. Just lying. Everything he said is a lie.
"Everything that he talked about me, the things that he said about me, when he was talking with Jose Mourinho, is a lie because nobody knew that I was going to Inter – even me.
"He’s a liar. About the pictures, he’s lying, so he’s a liar."