Mourinho established an emotional bond with a number of his players during his time as manager of the Italian giants and Materazzi insists it would be a dream to work alongside him.
The Portuguese has held talks with the board at the Santiago Bernabeu and agreed to leave in the summer following an unsuccessful campaign.
It is expected that the ‘Special One’ will return to Stamford Bridge, with interim manager Rafael Benitez due to leave his post once the side returns from a post-season tour of America.
Materazzi said: “I’d love to (be his assistant), it’d be a dream. In fact, you could call it an objective. I’d be working with the number one, so what could be better?
“Anyone who speaks ill of Mourinho just does it because of envy. I really liked his style of management, as he made us work a lot with the ball because he knows this sport is football.
“He always seeks success, as well as being an honest man. Honesty is one of the principle values in life, so why shouldn’t it be in sport?”