The 38-year-old is one of the three over-age players in
The trio were picked ahead of David Beckham, whose non-selection provoked a lot of debate.
Giggs will lead out Team GB for the first time when it faces Brazil at the Riverside Stadium on Friday, July 20.
"Obviously it is a tremendous honour to be part of the Olympics," Giggs said.
"Stuart has obviously given me the captaincy, which is even better so I am really looking forward to it.
"It is a unique experience and one from the start that I wanted to be part of when I got the opportunity.
"I think it just got more and more exciting as the Games got nearer and then when the squads were announced I was obviously really, really proud to be involved."
Despite never having played in a major international tournament with Wales, Giggs' credentials are impeccable, having won 12 Premier League titles, five FA Cups and two Champions League crowns.
He also won 64 caps for Wales before retiring from international football in 2007.
Pearce added: "I looked at the squad and I thought there are some good candidates there.
"Aaron Ramsey captains Wales, Micah Richards has captained Manchester City at times, Craig Bellamy for the experience he's had and one or two others within the camp as well.
"But I think Ryan is the standout captain amongst the group. He has got the respect of all the members of the group and I am quite looking forward to working with him and alongside him."
Ryan's roll of honour:
1973: Born Ryan Joseph Wilson on November 29 in Cardiff.
1990: Signs as a trainee with Manchester United in July and then as a professional at the start of December.
1991: Adopts mother's maiden name and becomes Ryan Giggs.
March - Makes United debut aged 17 as a substitute against Everton. Two months later he scores the winner against Manchester City at Old Trafford on his full debut.
October - Becomes the youngest footballer to represent Wales when he plays against Germany in Nuremberg aged 17 years and 322 days.
November - Wins his first piece of silverware with United as the Reds beat Red Star Belgrade to lift the UEFA Super Cup.
1992: Helps United lift League Cup and that season is voted PFA Young Player of the Year.
1993: Becomes first player to be named PFA Young Player of the Year twice.
Member of United side which ends the club's 26-year wait to win the league title.
1994: Helps United win the Premier League and FA Cup double for the first time in the club's history.
1996: Helps the Red Devils win the double for a second time.
1997: Wins a third league title in four years and in October scores a memorable goal in their 3-2 Champions League victory over Juventus at Old Trafford.
1998: Injures his hamstring in February and is out for six weeks as United finish the season empty-handed.
1999: Scores stunning winner in United's epic FA Cup semi-final replay victory over Arsenal at Villa Park in April. Helps the Reds complete an historic treble of European Cup, Premier League and FA Cup.
2000: Wins his sixth Premier League winners' medal in eight years.
2001: Collects his seventh league championship and 12th major honour in total.
July - Signs a new five-year contact worth around £50,000 a week. Sent off for the first time in his career for two bookable offences as Wales crash 3-2 in Norway.
2002: August 23: Nets 100th goal for United in all competitions with the team's second goal in league game at Chelsea.
2003: May - United are crowned champions again.
September - Giggs, along with Cristiano Ronaldo, charged with improper conduct by the Football Association following his involvement in confrontations with Arsenal players after a goalless draw at Old Trafford.
November - Giggs elbows Russia's Vadim Evseev in Euro 2004 play-off in Moscow, prompting the Russian football association to call for an immediate ban.
December - Giggs fined £7,500 and warned as to his future conduct at an FA disciplinary hearing into Old Trafford fracas. Then suspended for two matches for Evseev incident.
2004: May - United finish third in the table but Giggs lines up in the 3-0 FA Cup final victory over Millwall.
2007: May 6 - Wins ninth Premier League title with Manchester United.
May 30 - Announces retirement from international football.
October 16 - Signs new contract until end of June 2009.
May 11 - Equals Sir Bobby Charlton's appearance record for the club when he played his 758th game against Wigan.
May 21 - Breaks Sir Bobby Charlton's record after coming on as a substitute - and scoring a penalty in the dramatic shoot-out - as Manchester United beat Chelsea in the Champions League final.
2009: February 12 - Signs new deal with United, committing him to the club until June 2010.
April 26 - Voted Professional Footballers' Association player of the year.
May 16 - Helps United win the Premier League and becomes the first footballer to collect 11 top division English league title medals.
December 13 - Named BBC Sports Personality of the Year.
December 18 - Signs a one-year contract extension, keeping him at the club until June 2011,
December 31 - Named the Manchester United Player of the Decade.
2010: February - Wins the League Cup as United beat Aston Villa 2-1 in the final.
January 17 - Makes his 600th league appearance for United against Tottenham at White Hart Lane.
February - Signs a one-year contract extension.
March - Surpasses Charlton's Manchester United league appearance record by playing his 607th game against Liverpool.
May - Wins the Premier League title for a 12th time.
February - Signs one-year contract extension.
Makes his 900th appearance for United, scoring a last-minute winner in a 2-1 away win against Norwich.
June - Named as one of three over-age players in the Great Britain team for the Olympics.
July 8 - Confirmed as the captain of Team GB.
London 2012 has given women's football in the UK an 'unprecedented platform' on which to create a lasting legacy, according to the Football Association's head of national game Kelly Simmons.