Pearce, the former England captain and current boss of the Under-21s, was unveiled at Wembley along with Hope Powell, who was installed as head coach of the British women's team.
Pearce ideally wants a team of players from all the home nations even though the Scottish, Welsh and Irish football associations are all officially opposed to a Great Britain team as a concept, fearing it could jeopardise their independence with FIFA.
Welsh players, Tottenham's Gareth Bale and Arsenal's Aaron Ramsey, however, have already stated they want to play in the Games and the Welsh FA have said they would not stand in their way
Stuart Pearce: "I'm not going into this job looking only to select English players. It should be made up if at all possible of all the home nations.
"They will get in on form and fitness as at any football team in the country. I won't shut the door to anyone. If they suggest to me they want to be part of this and their form and fitness is good then it would be silly of me not to select players I thought were good enough.
"A lot of it will depend on the players' mentality. I think they will be very, very excited to be part of this showcase of football. Dialogue will come into it between myself and the federations and the managers concerned and I think support will be galvanised as the months go by and the tournament nears kick-off."
On whether 36-year-old David Beckham, who has expressed his desire to play in the Games, might be included as one of the three over-age players allowed in the 18-man squad of Under 23 players, Pearce would not be drawn.
Stuart Pearce: "I've no idea as yet.
"I've not seen him play recently. He's a bit too old for the Under 21s.
"Everyone will be up for selection. The FA have said to me the decision is totally yours, you pick who you deem right and proper to be part of this spectacle."