No-nonsense defender Materazzi retired from football at the end of 2011 after 10 years with Inter Milan, where he was part of the team that Mourinho famously coached to Champions League glory in 2010.
Mourinho left Inter for Spain after that success but his turbulent three-year spell with Real will conclude at the end of the season amid expectations of a return to Stamford Bridge.
Materazzi had one season in the Premier League with Everton in 1998-99 and says it would be a dream to come back for a second spell, this time alongside Mourinho.
"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?" Materazzi said.
"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?"