The Millennium Stadium will welcome Team GB Men's when they complete their Group A fixtures against Uruguay on August 1, having already played United Arab Emirates and Senegal at Old Trafford and Wembley Stadium respectively.
Football fans will also have the opportunity to watch Brazil, seeded as the "all-time top Olympic performer", play Egypt in Cardiff on July 26.
The men's team is made up of under-23 players with three over age players permitted per squad.
Cardiff's multi-sports venue will host 11 Olympic Football matches in total from July 25 and August 10 including the prestigious men's quarter-final and the Bronze Medal matches.
Millennium Stadium General Manager Gerry Toms said: "The official competition draw today was a massive day for football fans and for everyone in Wales as the official organisers announced the world-class teams we can expect in Cardiff this summer.
"We have secured some exciting matches both in the Women's and Men's draw. To have the opportunity to watch the likes of Brazil playing on our doorstep will be quite an honour."
With the countdown on until the eyes of the world are fixed on the Millennium Stadium, Mr Toms hopes that the people of Wales, not just the football fans, will show their support.
He said: "The London 2012 football tournament in Cardiff is a huge coup for Wales and for many sports fans it's a once-in-a-lifetime opportunity to be part of the Olympic Games.
"With 11 games taking place in our 74,500 capacity stadium there's plenty of chances to get involved and I hope that the Welsh fans come in their droves to be part of the exciting London 2012 action in their capital city this summer."
Great Britainwomen's coach Hope Powell has urged the general public to come out and support the host nation in the opening event of the Olympic Games at the Millennium Stadium.
Powell said: "With tickets going on sale again pretty soon then I'm sure there will be a big push from LOCOG (London's Olympic Organising Committee) and the British Olympic Association.
"It's the opening event of the game and we hope to have a big support.
"It was highlighted to me quite a while back when the dates were confirmed that the first game would be at the Millennium Stadium and I'm excited about that.
"It's a great opportunity for Women's Football to raise our profile and platform across the country and around the world because I believe there is no other event on that day.
"The press for us could be unprecedented which is a good thing. We can really showcase our sport throughout the country."
Great Britainalso play Cameroon at Wales' national stadium on Saturday, July 28.
OLYMPIC FOOTBALL - MEN'S GROUP STAGE DRAW
Group A: Great Britain, Uruguay, UAE, Senegal
Group B: Mexico, South Korea, Switzerland, Gabon
Group C: Brazil, Belarus, New Zealand, Egypt
Group D: Spain, Honduras, Japan, Morocco
OLYMPIC FOOTBALL - MEN'S SCHEDULE Millennium Stadium
August 1 - 19:45 - Great Britain v Uruguay - Millennium Stadium, Cardiff
August 1 - 17:00 - Mexico v Switzerland - Millennium Stadium, Cardiff
July 26 - 19:45 - Brazil v Egypt - Millennium Stadium, Cardiff
July 25- 16.00 Great Britain v New Zealand
July 25- 18.45 Cameroon v Brazil
July 28- 14.30 Great Britain v Cameroon
July 28- 17.15 New Zealand v Brazil
July 31- 14.30 Japan v South Africa
August 4 - 19:30 - Winner A v Runner-up B - Millennium Stadium, Cardiff
BRONZE MEDAL MATCH
August 10 - 19:45 - Millennium Stadium, Cardiff