Benitez has not been on good terms with the World Cup-winning Italian defender since he took charge of the treble-winning Inter Milan side in the summer of 2010, succeeding Jose Mourinho.
The Spaniard let rip at Materazzi in a press conference last week, calling him a liar 10 times - and in response Materazzi made fun of Benitez's weight: "So I'm a liar, he's slim then, so that gives reason to call me a liar.
"It pains me to say good luck to Chelsea but I will anyway. I feel sorry for their fans. If I was president of a club, I would not trust him with my team."
The hostilities between the pair had been reignited by Materazzi early this month in an interview with France Football when he 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."
Materazzi is perhaps best known for being head-butted by Zinedine Zidane in the 2006 World Cup final – such an iconic football moment that it has been celebrated as a work of art in Paris.