Thomas Bjorn and Catriona Matthew will make up the 'Captains Team' when the innovative GolfSixes event returns to the European Tour schedule in May.
Ryder Cup captain Bjorn and Solheim Cup skipper Matthew will join forces to become the first male and female professionals to play together in a competitive match-play format.
Bjorn and Matthew are among four wildcard selections for the second edition of the 16-team tournament, which will be staged at the Centurion Club in St Albans on May 5 and 6.
Georgia Hall and Charley Hull will represent the 'England Women's Team', while Mel Reid and Suzann Pettersen have been selected for the 'European Women's Team'.
Lucas Bjerregaard and Thorbjorn Olesen will attempt to defend Denmark's title and the final wild card team will be announced late next month, with 11 men's national teams qualifying automatically from the European Tour's Category Ranking List.
Bjorn said: "I am really excited about playing GolfSixes. There are so many 72-hole tournaments around the world that there has to be room for something else which puts a different spin on golf and brings more interest.
"This is not your normal golf tournament where everyone is very serious and has their heads down. This is completely different, it's more about having fun and portraying the game in a good way."
Matthew stated: "I was delighted when Thomas asked me to play GolfSixes. I had to move my schedule around a little bit but the moment I heard about the chance to play, I definitely wanted to be part of it.
"The fact it is something different for golf is great - in terms of the round robin match play format then head to head matches, in addition to the men and women playing together of course. All Tours are trying to think of ways to make golf different and encourage a new and younger audience and so I think this whole concept is very exciting."