Argentina international Mascherano was signed for Liverpool from West Ham United by Benitez in January 2007 and left Anfield for Barcelona in August 2010, just two months after the Spaniard's departure as Reds manager.
Benitez is now in charge of Napoli and reports have linked Mascherano with a January move to the Serie A club.
Napoli president Aurelio de Laurentiis last week stated that he is 'not interested' in signing Mascherano, instead suggesting Lyon midfielder Maxime Gonalons is the type of player he would be keen to take to the club.
Mascherano, himself, is not looking to leave Barcelona, but confirmed he retains great affection for Benitez following their time together at Liverpool.
"I like Serie A very much, the level is high and you can see beautiful games," Mascherano told La Gazzetta dello Sport.
"I'm often in touch with Rafa Benitez, we have a great relationship.
"I'm a grateful person and I remember that Rafa took me from West Ham, where I did not play, and gave me confidence at Liverpool in a team full of great midfielders.
"I'd love to work with him again someday and he knows it. But today I'm at Barcelona and I'm fine there. In the future, we will see."