Pettersen, who holed the winning putt for Matthew in the 2019 match at Gleneagles, will take up the reins for the 2023 contest at Finca Cortesín on Spain’s Costa del Sol.
“This is the biggest honour of my career,” said Pettersen, a two-time major champion who represented Europe nine times as a player and twice as a vice-captain.
“My best golfing memories are from the Solheim Cup. You are out there with your team mates, your friends, and you all work for one goal. You fight for your friends and you share incredibly precious moments.
“I have played with and under many wonderful captains since I made my debut in the competition 19 years ago. Every Solheim has been special in its own way. You make friendships for life and memories you’ll never forget.
“Every captain is different and brings their unique skills to the table. I am very much looking forward to bringing my experience to the role and working hard over the next 22 months to defend the Cup on Spanish soil.”
Pettersen has been part of five triumphs, including the past two victories at Gleneagles in and at Inverness Club in Ohio in September.
At Gleneagles, she was picked by Matthew following an 18-month maternity leave and vindicated that bold decision in style by converting a seven-foot birdie putt in the deciding singles match.
The 14.5-13.5 victory tied for the closest winning margin in Solheim Cup history and Pettersen retired from competition immediately afterwards, saying “It doesn’t get any better than this.”
Alexandra Armas, chief executive of the Ladies European Tour, said: “We are delighted that Suzann has accepted the role of captain for the 2023 Solheim Cup.
“She has been the heart and soul of the European team for almost 20 years and, with 21 points earned from nine appearances, her record speaks for itself.
“With her passion for the Solheim Cup, her love for the game of golf and her competitive fire, she will be an inspiration to the team and to fans around the world.”