“After much consideration, I have decided to join several of my fellow professionals and play in the LIV invitational series,” the 46-year-old Swede said in a statement.
Stenson said he was “hugely disappointed” not to be able to maintain his role as captain for the next Ryder Cup to be played in Italy next year.
“It is a shame to witness the significant uncertainty surrounding the Ryder Cup and who will be eligible to play, etc. I hope a resolution between the tours and its members is reached soon,” he added.
The move to strip Stenson of the captaincy will deepen the rifts in the sport, with a growing number of big stars defecting to the cash-rich new circuit in defiance of the established tours.
Ryder Cup Europe said in a statement that Stenson’s tenure as skipper for the biennial competition against the United States in Rome had been brought to an end “with immediate effect”.
“In light of decisions made by Henrik in relation to his personal circumstances, it has become clear that he will not be able to fulfil certain contractual obligations to Ryder Cup Europe,” it said.
The statement added that confirmation of a new captain for the 2023 tournament would be made in “due course”.
Stenson has now joined fellow Ryder Cup stars Lee Westwood, Ian Poulter and Sergio Garcia in jumping ship to the LIV series.
The US team next year looks likely to be without players of the calibre of Dustin Johnson, Brooks Koepka, Patrick Reed and Bryson DeChambeau, who have all been hit with indefinite bans by the PGA Tour and will therefore be ineligible to play.
Stenson, the 2016 British Open champion, reached a career high of number two in the world but has since slumped to 171 in the rankings.
“Clearly a part of my decision to play in LIV golf events has been commercially driven but the format, schedule and calibre of players were also significant factors,” said Stenson.
Stenson’s appointment as skipper of Team Europe in March had appeared to end speculation about his involvement in the Saudi-backed breakaway series as he insisted he was fully committed to the role.
But after missing the cut at last week’s British Open, Stenson admitted his upcoming schedule was “undecided”.
European players must be members of the DP World Tour, formerly known as the European Tour, to be eligible to compete for Team Europe in the Ryder Cup.
The tour last month banned members who played in the inaugural LIV event in England for three tournaments and hit them with a heavy fine while the US PGA Tour banned those who made the jump.
Donald Trump on Monday urged golfers to “take the money” and sign with LIV Golf.
The former US president, who is hosting LIV events at two of his golf courses this year, said in a post on his Truth Social network that players should not hesitate to abandon the US PGA Tour, which he branded “disloyal”.
LIV Golf, which is fronted by Australian great Greg Norman, is bankrolled by Saudi Arabia’s Public Investment Fund.
Human Rights groups have criticised the venture, saying it is a “sportswashing” venture being used to boost Saudi Arabia’s international reputation.
The third 54-hole LIV event of the season will tee off at Trump National Golf Club Bedminster, New Jersey, on July 29.
The field for the tournament includes England’s former world number three Paul Casey, who will tee off alongside 11 major champions, including Stenson - who was officially confirmed yesterday along with Americans Jason Kokrak and Charles Howell to complete the field.
Former Masters champion Hideki Matsuyama has been linked with a move to LIV Golf, with three more signings to be named in the coming days.
Europe will be aiming to wrestle back the Ryder Cup from the United States when the two teams meet at the Marco Simone Golf and Country Club from Sept 29 next year.
Potential replacement captains include Thomas Bjorn, who led Europe to victory in France in 2018, and England’s Luke Donald.