Fleetwood and Molinari the captains for Europe's Ryder Cup warm-up
The Hero Cup will take place in Abu Dhabi from January 13-15 between two teams of 10, with England's Fleetwood leading Great Britain and Ireland against a Continental Europe side skippered by Italy's 2018 British Open champion Molinari.
The tournament will feature foursomes, fourballs and singles matches, with all 20 players taking part in each session in an event overseen by Luke Donald (44), the captain of the Europe team at next year's Ryder Cup in Italy.
Molinari and Fleetwood won all four of their matches together in the 2018 Ryder Cup in Paris as Europe won the trophy.
But the most recent edition of the biennial event, the Covid-delayed 2021 competition, saw the United States thrash Europe 19 points to nine at Whistling Straits in Wisconsin.
The Hero Cup effectively replaces the Seve Cup, a similar competition, which was held eight times from 2000-2013.
Molinari welcomed the new event by saying in a statement: "The Hero Cup is a great idea and will be a very good way for European players to get some more experience of playing in team match play. I definitely felt like it benefited me when I played in similar events in the past.
"Hopefully as captains Tommy and I can bring some of our own experience of team golf to help the other players and we are looking forward to working with Luke on this exciting new concept ahead of a big year for European golf with the Ryder Cup taking place in my home country."
Fleetwood added: "Fran and I obviously get on very well so I am sure it will feel a little strange at first being opposing captains, but I think the Hero Cup is a fantastic way for players to compete in team match play, which is something both of us have always relished."
The two teams will be confirmed following the conclusion of the 2022 DP World Tour Championship in Dubai in November, with DP tour rankings taken into account in the selection process.
The DP World Tour was previously known as the European Tour.
Next year's Ryder Cup takes place in Rome from September 29 to October 1.
