Olympic tennis manager Todd Woodbridge said “we have a good chance of something happening” in London, though he conceded the Australians were not medal favourites.
“It will be the pinnacle of the Olympics to be playing at the home of tennis at Wimbledon,” said Woodbridge.
Stosur, ranked 5th in the world, automatically qualified for the singles event and will also contest the doubles title, pairing up with 108th-ranked Casey Dellacqua.
“The Olympics are really special and I love being a part of a team and competing for my country,” said Stosur, representing Australia at her third games.
“The memories I have from past Olympics are some of my most cherished, so I am really excited for London.”
Jarmila Gajdosova (76) and Anastasia Rodionova (133) also got a doubles call-up.
Rising star Tomic, 28th in the world at just 19, won automatic selection in the men’s singles along with wildcard Lleyton Hewitt, who bombed out of Wimbledon in the first round this week, ten years after winning the title.
Tomic is likely to drop from the top 30 after a shock first-round exit at Wimbledon against Belgian wildcard David Goffin, continuing a woeful run which has seen him fail to pass the second round in 11 of his last 12 tournaments.
Australia was not offered a men’s doubles berth at the London Games, drawing the ire of injury-plagued Hewitt, 31.
“I’m disappointed not to make the doubles. I guess playing as much Davis Cup doesn’t count for anything,” the veteran said after his Wimbledon loss.
Mixed doubles will return to the Olympic program in 2012 for the first time since 1924 but pairings will not be determined until during the Games.
Australian Olympic officials said two additional male players “may still receive positions”, with the International Tennis Federation allocating quota places until July 20.