The match play contest will be played at Abu Dhabi Golf Club from January 13-15. Fleetwood and Molinari will each select nine players for their teams before filling the 10th place themselves.
The other nine players on each team will be revealed in early December. Fleetwood and Molinari, once known as 'Moliwood' at the 2018 Ryder Cup, will work alongside Team Europe captain Luke Donald who will preside over the event.
The Englishman and the Italian won all four of their matches together as a pair in Paris four years ago. This was also the year that Molinari won The Open Championship at Carnoustie.
Selection will be based on the DP World Tour Rankings with the match itself consisting of one session of foursomes, one session of fourballs and one session of singles. All 20 players take part in each session and members of the winning team will each bank $125,000.
"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," Fleetwood said.
"Abu Dhabi has been pretty good to me over the years so hopefully that will continue in January and I look forward to working closely with Fran and Luke, as well as all the players."
"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," Molinari added.
"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."
"I am grateful to Tommy and Fran for supporting this overall concept and for accepting the roles of playing Captains. Their wealth of experience, both individually in the wider team environment, will be a huge asset for the other 18 players who will be part of this event in Abu Dhabi in January," Donald said.
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