The 49-year-old Pearce, who has been in charge of England Under-21s since 2007, was chosen to lead a combined British team at an Olympics for the first time since the Rome Games of 1960.
England's women's coach Hope Powell will coach the first British women's team to take part.
Pearce will, in theory, select mainly under-23 players from England, Wales, Scotland and Northern Ireland although the participation of a British team has proved problematic as the other home nations fear taking part could jeopardise their independent status within FIFA, world football's governing body.
Pearce, however, told reporters at Wembley Stadium that he would pick players from all four home nations on merit at the time of the Games.
"I am certainly not going into this job looking only to select English players," he said.
"If at all possible the squad will have players from all four home nations and all the home nations should come forward and put their players up for selection.
"A lot of it will depend on the players mentality. If the players want to be part of the squad that will be fantastic.
"If you look at role models in the past like Lionel Messi - he actually went to court to fight his club to get released to go the Olympics.
"The tournament will be a showcase of football in a major sporting event in this country and I will not shut the door to anybody."
Former England international David Beckham, who will be 37 by the time of the Olympics, has expressed his interest in being included as one of the three over-age players and Pearce did not rule him out.
"But I've not seen him play recently, he's a bit too old for the under-21s," Pearce joked.
Wales' outstanding young players Gareth Bale of Tottenham Hotspur and Aaron Ramsey of Arsenal have also stated their willingness to play.
HISTORIC AGREEMENT
The formation of the first British team to take part in the Olympics finals for 52 years has been complicated.
In June, the BOA angered Northern Ireland, Scotland and Wales by announcing an "historic agreement" for Britain to field a united team for the first time in 52 years.
The three home associations, worried about their national identities in world football, issued a joint statement rejecting the BOA's statement and voiced their opposition to their players taking part in the Games.
FA Chairman David Bernstein stressed that FIFA had said many times that their independent positions were secure.
Pearce, who spent most of his playing career with Nottingham Forest where he earned a reputation as a hard man, played for England 78 times and was an integral part of the squad that reached the semi-finals of Euro 96, the last major football tournament staged in England.
"I was fortunate enough to be part of that so I know how special it is to play for your country on home soil at a major tournament," he said.
