Chelsea are favourites to re-sign their former boss, with Rafael Benitez's short-term contract up at the end of the season.
Tottenham manager Villas-Boas worked under his Portuguese countryman at Porto, Chelsea and Inter Milan, and he believes Mourinho is likely to have a position lined up.
Villas-Boas said: "He obviously wants to come back to England, whether he has a club aligned or not, we never know.
"It's extremely unlikely when someone makes it that public that something is not set out already but he is a great addition to the Premier League. He has a wonderful history in this league and I think it will be spectacular to have him back."
Mourinho has won a significant haul of trophies at all his clubs but has found it most difficult at Madrid.
Defeat over two legs against Borussia Dortmund in the semi-finals means the Champions League will once again elude the Spaniards this season, and Villas-Boas acknowledged Mourinho probably has not lived up to expectations.
The Spurs boss said: "When he left (England) he wasn't that well loved by a few of you guys (the media) and that was something we talked about.
"He was loved in all the clubs where he has won titles, in Real Madrid the same.
"There is maximum respect for what he has achieved, but for it to be at the level of Real Madrid's expectancy, we will never know. Probably not, but he certainly has won a league against a dream Barcelona team, which is a great achievement."
West Brom manager Steve Clarke and Swansea's Michael Laudrup would both welcome Mourinho's return to the Premier League.
Clarke was assistant manager to the 50-year-old at Chelsea, but he insisted: "I don't know if he's coming or not, that's the truth.
"I know he was happy here because he had a good job at a good club and we were successful. That's what he likes, he likes to win football matches wherever he is.
"If he comes back, it's great for the Premier League. If he does come back and we get the chance to play against him that would be great."
Laudrup, a former Real Madrid midfielder, added: "To have good managers in a top league is always good, and there will be a lot of nice press conferences for the media to look forward to.
"He is a good manager, you just need to look at his CV and what he has achieved with all his clubs, so for him to return to Chelsea would be good for the Premier League."
Reading's Nigel Adkins also believes Mourinho's return would be a boost for the English game, saying: "Jose Mourinho is a character and people love watching him. His teams consistently play winning football.
"For a character like that to be in the Premier League can only be good for English football."