The Welshman is one of Team GB's best hopes for a gold medal on the track as he looks to add the Olympic title to his world, European and Commonwealth victories.
"It is an incredible privilege to be asked to captain the British athletics team at any time, but to be given the honour at a home Olympic Games is just incredible," said the 26-year-old.
Greene, who has been chosen ahead of athletes such as Jessica Ennis and Mo Farah, will captain a 78-strong team, having proven himself as one of the nation's best athletes over the last two years. The choice also ensured there would be no repeat of the "Plastic Brits" controversy which overshadowed the World Indoor Championships in March, when United States-born 100m hurdler Tiffany Porter was named team captain.
Porter was asked at the pre-championships press conference to recite the first verse of 'God Save the Queen', but declined, alsthough she insisted she did know it. Porter is one of a handful of athletes in the Olympic team dubbed "Plastic Brits", because they switched allegiance to represent Britain.
Another is Havana-born triple jumper Yamile Aldama, who had been touted as a possible team captain for London 2012. Aldama, who is the world indoor champion, competed for Cuba at the 2000 Olympics and for Sudan four years later. But she she qualifies for Team GB as she is married to a Scot and finally gained British citizenship in 2010 almost 10 years after her initial application.
Greene captained the team last year at the European Team Championships in Sweden. The former Swansea City youth-team footballer, is one of the most confident athletes on the team. "We have a great team spirit in the camp, which will make giving my speech much easier," he said.
"I think our team is one of the strongest in history and I believe that we can go out and do Britain proud and I intend to lead by example."
Charles van Commenee, the UK Athletics head coach, last night endorsed the decision to appoint Greene. "Dai was a stand out candidate for the London 2012 captaincy. He is a very professional athlete who is both liked and respected by the rest of the team," said the Dutchman.
"He knows what it takes to win at the highest level and that is a valuable experience to share with the team. I know we can also rely on Dai to inspire his team-mates and I wouldn't be surprised if he raised a few laughs during his speech along the way."
Greene won the European and Commonwealth titles in 2010 and proved his credentials on the global stage by winning World Championship gold in Daegu last summer. His form and fitness had been questioned after a slow start to the season, caused by a knee operation and illness, but he dismissed any doubts with a personal best at the Diamond League meeting in Paris last Friday. He ran 47.84 seconds, finishing second to world No.1 Javier Culson.
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