The 33-year-old worked under the self-styled 'special one' at Chelsea and followed the same route to west London after a spell at Porto.
Villas-Boas said his focus is to build a team ethic at Stamford Bridge.
"I was appointed for human qualities," Villas-Boas told Chelsea TV.
"I don't see the game as a one-man show, I see the game as the getting together of collective ideas and good players.
Continue reading the main story 1977: Born in Porto on 17 October1993: Works as a trainee under Sir Bobby Robson at Porto1994: Achieves Uefa C coaching licence in Scotland2002: Becomes part of Jose Mourinho's staff at Porto2004: Follows Mourinho to Chelsea2008: Moves with Mourinho to Inter Milan2009: Appointed manager of Academica2010: Named Porto boss 2011: Wins league, cup and Europa League in first season"The most important thing is to motivate the players to get their ambitions right, to reflect again on what the club has achieved in the last six years and we need to keep this route to success.
"We are a technical staff that focuses a lot on unlocking potential and that incentivises a lot of freedom of choice because in the end, when the players are on the pitch, they face different situations that they have to solve without the help of their manager.
"This is the kind of stimulus that we want the players to have, responsibility and making decisions, because in the end the game is decided by them on the pitch.
"It is a clashing together of two good organisations and in the end it is the relationship between all of our players that can lead us to success, and that is what I want to work on."
Last season, Villas-Boas enjoyed huge success with Porto in his native Portugal, winning the league and League Cup double and also guiding the team to Europa League triumph.
It was this that marked him out as the stand-out candidate for Chelsea, who were willing to part with ?13.3m to activate the release clause in his Porto contract and make him their new manager.
The move to west London mirrors that of former Blues boss Mourinho, who also enjoyed huge success at Porto - winning the domestic league and Champions League in his final season before he was lured to west London by Chelsea owner Roman Abramovich.
The task facing Andre Villas-Boas"I think there is no way you can avoid comparison, it is something that is the interest of the media. I didn't take the Porto job nor the Chelsea job because Jose made the same steps," added Villas-Boas, who followed Mourinho to Inter Milan after he left Chelsea in 2007.
"They are two of the most sought-after clubs in the world and in the end I had the opportunity and was able to make them find something in me that they thought would continue their route to success.
"Coaching was not a kind of obsession [for me] and neither did I use Jose as the way to arrive into this path, it was something that happened naturally."
Villas-Boas moves to Chelsea following the departure of Italian Carlo Ancelotti, who was sacked at the end of a trophyless campaign last season, despite him having won two trophies in his maiden season the previous year.
The new manager is well-aware of the expectations placed on him in his new role.
"Chelsea is a club that in the last six years has achieved so much and people are expecting us to be the same way," he added.
"There is not going to be more or less tolerance for me if I am not successful so this is the challenge I face and I feel confident that we can motivate everybody, not only the players but also the structure.
"I feel confident I can respond to the ambitions of the supporters and the ambitions of the owner and the administration."
On Tuesday, Porto president Jorge Pinto da Costa told reporters that he was proud of the clubs' achievements under Villas-Boas but that they will now begin the process of moving on, which they have done by quickly promoting assistant Vitor Pereira to head coach.
However, the mood amongst the Porto fans is less positive.
"Despite the 'no hard feelings' official line from FC Porto, Villas-Boas's departure has not gone down at all well in Portugal's second city," reported BBC Sport's Matt Slater in Porto.
"Just another money-obsessed careerist would be the polite translation of much of what I've heard here and he already has a new nickname, Andre Libras-Boas: Andre Good-Pounds.
"The fans were looking forward to taking on Barcelona in the European Super Cup in August and a crack at the Champions League. Now they are panicking about pre-season starting next week and which players AVB is taking with him."
Villas-Boas looks likely to join Chelsea Chelsea target Andre Villas-Boas has tendered his resignation as Porto coach, the Portuguese club have said.