The seventh-seeded Indian duo of Mahesh Bhupathi and Rohan Bopanna, whose insistence to play together sparked off a selection storm in the build-up to the Olympics, open their campaign in the Olympic men's doubles against Max Mirnyi and Alexander Bury of Belarus.
The event will be held at Wimbledon from July 28.
Seasoned pro Leander Paes and his unfancied partner Vishnu Vardhan take on Julien jean Rojer and Robin Haase of the Netherlands.
In the women's doubles, Sania Mirza and Rushmi Chakravarthi clash with the Taipei duo of Su Wei Hsieh and Chia-Jung Chuang in the opening round.
Somdev Devvarman, who got a wild card, will launch his campaign against Jarkko Nieminen of Finland in the men's singles.
If he overcomes his first round opponent, he will take on the winner of the match between third seeded Andy Murray of England and Stanisias Wawrinka of Switzerland.
The No. 1 seed in the men's singles, Roger Federer, who won the doubles gold medal with Swiss teammate Wawrinka in Beijing, will face Alejandro Falla in the opening round.
The second seeded Novak Djokovic, who won the singles bronze medal in Beijing, isdrawn against Fabio Fognini.
The Serb leads their head-to-head series 2-1, including straight set wins in their last two meetings.
Murray, seeded No. 3, is in the same half of the draw as Djokovic and has been handed a tough first round assignment against Wawrinka, while No. 4 seed David Ferrer takes on Vasek Pospisil.
In the women's singles, both the Williams sisters face tough opponents in the first round.
Serena, seeded No. 4, will play Jelena Jankovic, while Venus will take on No. 9 seed Sara Errani.
Serena and Venus are two-time doubles gold medallists, while Venus also won the singles gold medal in Sydney.
Altogether 44 countries are being represented at The All England Club. There is a 64-draw for the men's and women's singles, with 16 players seeded in each event, and a 32-draw for the men's and women's doubles, with eight teams seeded in each event.
The mixed doubles, which is making a return to the Olympics as a medal sport for the first time since Paris 1924, will have a 16-team draw, with four seeded. The draw for the mixed doubles is being held mid-way through the tennis event on July 31.
Entry to the mixed doubles is based on each pair's combined ranking.
Players can use either their singles or doubles ranking to qualify, whichever is highest, and a maximum of two teams per country are permitted.
There are 12 Direct Acceptances into the mixed doubles, with the remaining four spots being filled by ITF places.