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Italian Di Matteo played for the Londoners between 1996 and 2002 when injury forced his retirement at the age of 31.
Villas-Boas has also recruited Jose Mario Rocha, a 48-year-old fitness expert who worked alongside the Portuguese at his previous clubs Porto and Academica.
Another new face is Daniel Sousa who will become head opposition scout, the role occupied by Villas-Boas in his first spell at the club under Jose Mourinho between 2004 and 2007.
Sousa worked alongside Villas-Boas at his two former clubs. Steve Holland, Chelsea's reserve coach last season, will also step up to work with the senior squad.
Di Matteo scored FA Cup final goals in 1997 and 2000, the first of which set a Wembley record for the earliest in a final after just 43 seconds.
The former Italy international was previously manager of Milton Keynes Dons and West Bromwich Albion, the club he left in February.
Villas-Boas said: "If you see the technical staff in front of me, and my appointment of Roberto, these are people who like the quality of the game and have a philosophy.
"It's not just a case of winning it's a case of flair.
"Everyone likes attacking football and the Premier League has a certain amount of goals in every game and it should be an entertaining game for the fans and that is what we will look to do."
The 33-year-old is no stranger to Stamford Bridge or to senior members of the dressing room, having been part of Jose Mourinho's backroom staff. However, now returning as the man charged by owner Roman Abramovich with delivering the Champions League, the young Portuguese coach will need to hit the ground running.
However, he refused to repeat the hyperbole of his mentor as he branded himself "the group one".
Mourinho famously dubbed himself as the 'special one' when he was introduced to the media for the first time as Blues boss, but Villas-Boas, who worked under his Portuguese compatriot at Stamford Bridge, opted for a different approach.
When asked what title he would like the media to give him, he replied: "The title... I will wait for you guys to give it me when I am successful. I hope I am and you can give me a good title."
He added: "This is not a one-man show, this is about creating empathy, ambition and motivation in everybody.
"Maybe I should be called the group one as I want to group people together and be successful."
Villas-Boas also side-stepped questions about how he may look to take on established Premier League managers such as Manchester United boss Sir Alex Ferguson.
"It's not just a question of me taking on Sir Alex, it's a top club like Chelsea challenging for the title," he said.
"We need to be up there from the beginning and it is not one man against the other, it's about trying to build something that can make us powerful, and help us threaten for the title as we have in the past."