Former Blues midfielder Di Matteo was confirmed on Wednesday morning as Villas-Boas' number two during the latter's official unveiling as Blues boss.
Di Matteo, 41, spent six years at Stamford Bridge as a player but was a surprise choice to work under 33-year-old Villas-Boas.
Steve Holland was also promoted from his job as reserve-team manager to the backroom team, which includes Jose Mario Rocha and Daniel Sousa, who Villas-Boas brought with him from Porto.
Di Matteo had been out of work since being sacked by West Brom in February, despite leading them into the Premier League and earning praise for the quality of their football.
Chelsea owner Abramovich is thought to want Chelsea to play more expansively and Villas-Boas said: "From the technical staff you see in front of me, you see Roberto as number two and the way his team played last year, and all my technical staff who followed me from before and Steve Holland, these are people who like the quality of the game, the philosophy of the game. They like to play well.
"It's not just a question of winning, but winning with a certain flair. Everyone likes attacking football.
"The Premier League is the most entertaining league in the world.
"A philosophy is that it should be an entertaining game for the fans."
He added: "We are proud defenders of the beauty of the game. It makes no sense for us to get into a club like Chelsea and play dreadful football.
"This is why this technical staff was picked, based on a philosophy of playing well and as a team."
New appointments inevitably mean departures and among those who have been jettisoned are assistant first-team coach Paul Clement, club doctor Bryan English and fitness coach Glen Driscoll.
Villas-Boas said: "The people who left leave with tremendous success, and we pay respect to them.
"We want to create empathy between the departments, so I've been approaching people over the last week, feeling people, presenting myself to people.
"Changes happen in any structure."
Source: Team Talk
Source: Team Talk