They made the announcement in a statement to the Portuguese Securities Market Commission.
Villas-Boas, 33, has been linked with Chelsea in recent days following the sacking of Carlo Ancelotti in May.
Porto insisted on Monday that Villas-Boas could leave if a rival club paid ?13.2m to activate a release clause in his contract.
"FC Porto was today notified of the intention of Andre Villas-Boas to resign from his contract with the club by triggering the release clause immediately," read a Porto statement.
"The contract will be terminated once the required amount is paid."
The Lusa news agency had reported earlier on Tuesday that Villas-Boas would pay the ?13.2m himself.
Villas-Boas guided Porto to a treble last season, winning both the league and league cup as well as the Europa League.
Porto ended last season unbeaten in the league, with 27 wins in 30 matches, becoming only the second Portuguese club to finish a league season unbeaten, after Benfica in 1972-73.
Continue reading the main story Has an English grandmother and boasts a count and a baron among his relativesInvited to work as a trainee with Porto's youth-team coaches in 1994 by Sir Bobby RobsonWould become youngest current manager in Premier League at 33 if he ends up taking over at ChelseaA scout for compatriot Jose Mourinho at Porto, Chelsea and Inter Milan, Villas-Boas began his managerial career with Portuguese club Academica in October 2009.
Academica were winless and bottom of the first division at the time but finished the season in 11th place.
They also reached a Portuguese League Cup semi-final before Villas-Boas left to take over at Porto in June 2010.
Villas-Boas, who speaks fluent English, also worked with Sir Bobby Robson during the former England manager's spell in charge of Porto.
Ancelotti was sacked by Chelsea following a season without any silverware, with the London club finishing runners-up to Manchester United in the Premier League.
Numerous candidates have been touted as possible replacements for the Italian, among them Turkey boss Guus Hiddink, Villas-Boas and former Fulham, Manchester City and Blackburn boss Mark Hughes.
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