It is a moment of history and an opportunity for Chris Finch's side to prove their capabilities on the grandest stage of all.
GB forward Luol Deng hopes to inspire a generation: "I want the Olympics to mark the beginning of when basketball became a well known sport in Britain. Where basketball courts are filled with kids and centres are regularly teaching basketball and the kids have something to look forward when they turn 16 or 17.
"The Olympics marks the start of that for us and for the women's team and we want to make the country proud."
GB assistant coach Nick Nurse believes that this is the best team that British Basketball has ever put together, however says that the role players must stand up and make significant contributions.
"Luol is obviously going to be a focal point, offensively and defensively," Nurse admitted. "He's a world-class player. He'll have the ball. But we've played a number of games without him, trying to get our guys experience.
"When he's not out there, they've got to do a little more, as do the experienced guys. But when the games come on, I'd imagine he's going to take a fair amount of shots. He's going to make a fair number of plays for his teammates. That's his biggest strength. He's a playmaker and when he draws so much attention, it leaves openings for other players," Nurse added.
The GB players will also be playing with a point to prove to the world after making their way steadily up the rankings in the wake for London being awarded the Olympics in 2005 and British Basketball being formed a year later.
Stirling-born Kieron Achara said: "We're gelling now. We know each other. We know what to expect. And the fact we had to qualify for our own Olympics proves that we're not taken lightly. We have a little chip on our shoulders and we want to prove ourselves."
Great Britain tip off against Russia, who booked their Olympic spot earlier this month through the FIBA Qualifying Tournament in Venezuela, in London on Sunday at 8pm, with the hosts also looking to extract a little vengeance after a Deng-less side lost twice to their Group B rivals in the build-up to the Games last month.
"These warm-ups have been good for us," Deng said. "We've played against the top teams and competed against them well. Coach has used different rotations and systems so that we got a good team chemistry and going into our first Olympic Games, everything is good."
GB also face Russia, China, Australia and Spain in their preliminary round group with the top four finishers advancing into the quarter-finals.