Villas-Boas tendered his resignation with the Portuguese and Europa League champions earlier on Tuesday to pave the way for his move to Stamford Bridge.
That resignation has now been accepted after Porto received compensation, which is reported to be ?13.2million, and Villas-Boas is set to hold talks with Chelsea on Wednesday.
"We note that the release clause of Andre Villas-Boas has been activated," a Chelsea club statement read.
"We can at this time confirm our interest in him and hope to reach agreement with him on personal terms and make a further announcement in the near future."
Porto have also confirmed that Vitor Pereira has been appointed as their new coach and successor to Villas-Boas on a two-year contract.
A statement from Porto to the Portuguese Securities Market Commission read: "FC Porto, in accordance with Article 248 paragraph 1 of the Securities Code, hereby informs the market they have received from Mr Andre Villas-Boas the amount provided for in clause to terminate his employment contract."
The statement added that all that remained to settle were the formalities of the termination of the contract.
Porto added on their official website: "The amount has been deposited on the termination clause of the work contract of Andre Villas-Boas."
Discussions between Villas-Boas and Chelsea in London will focus on salary, which is understood to be ?90,000-a-week, and his determination to bring members of his backroom staff to England.
Fitness coach Jose Mario Rocha is an important colleague of the Porto native after they also worked together at former club Academica Coimbra.
Opposition scout Daniel Sousa is another thought to be wanted by Villas-Boas, who worked as an opposition scout under Jose Mourinho at Chelsea, when he agrees a probable three-year contract.
Chelsea have been looking for a new boss since owner Roman Abramovich decided to sack Carlo Ancelotti on the final day of last season following a trophyless campaign.
Turkey boss Guus Hiddink was favourite to return to the managerial position he occupied on a short-term basis in 2009, or even take up a role as director of football.
But the Dutchman is now not expected to move back to Chelsea and has been linked with the job at Inter Milan.
Source: Team Talk
Source: Team Talk