Nestor, Vasek Pospisil, Raonic and Aleksandra Wozniak were nominated for selection to Canada's Olympic team for London on Wednesday.
Nestor, who won Canada's only gold medal in tennis with Sebastien Lareau in 2000, will team up with Vancouver's Pospisil in doubles on the All England Club in Wimbledon, the Olympic venue for the sport.
Raonic, from Thornhill, Ont., and Wozniak, from Blainville, Que., will play singles.
"My dream came true today," Wozniak said on a conference call. "I'm very excited and I'm sure that I'll be feeling many emotions once I'm there. It's definitely going to be a different atmosphere than playing at the big Grand Slams on the WTA Tour.
"It's something where you'll be with the best athletes from around the world in all different sports."
Each of the world's top 10 doubles players received direct entry into the Games, with a partner of their choice.
Nestor, the world's No. 1-ranked doubles player from Toronto, and Pospisil hold a 2-0 Davis Cup record, including a key victory against Grand Slam champions Jonathan Erlich and Andy Ram during Canada's World Group play-off versus Israel last September.
"I'm very proud to be in a position where I can represent my country and hopefully bring back another medal," said Nestor, who will make his fifth consecutive Olympic appearance. "It was quite a special feat winning Olympic gold in Sydney in 2000 and with the growth of tennis in our country, we all can have a chance to make Canada proud."
The top 56 singles players received direct entry into the Games. Raonic is No. 21 in the world while Wozniak's third-round appearance at the French Open lifted her to the cut-off point at No. 56. Both will make their Olympic debuts.
The International Tennis Federation will announce the official list of entries on June 28. Additional nominations for players who did not make the rankings cut-off can be submitted to the ITF to be considered for ITF places.
A total of six men and six women per country are allowed to participate with a maximum of four singles players, two doubles teams and two mixed doubles teams per draw.
The Olympic tennis event is July 28-Aug. 5.
Immediately following the London tennis event, Canadian players will return to Montreal and Toronto to play Rogers Cup, August 4-13. Nestor, Pospisil and Raonic will play at Rexall Centre in Toronto while Wozniak will play at Uniprix Stadium in Montreal.