Emile Gomis scored 22 points as France beat Australia 74-70 in over-time Monday, setting back the Opals' quest for women's basketball gold after three Olympic silver medals in a row.
French captain Celine Dumerc scored 13 points while Sandrine Gruda and Edwige Lawson-Wade each added 11 and Isabelle Yacoubou contributed 10 points and seven rebounds.
"It was a big, big victory because it was against a big team like Australia," Dumerc said. "It was not a target for us at the beginning of the tournament but we played with desire and energy to get the win."
It was the first victory for France over Australia in seven meetings at the Olympics or world championships.
"Playing Australia is a really tough game physically. The Australian team are physical monsters," Yacoubou said. "We had to sacrifice ourselves on defence."
Women's NBA star centre Lauren Jackson managed only 13 points and six rebounds before fouling out. Aussie Liz Cambage had 12 points before fouling out as well.
"It was a great game but for us it was a bit of a shame," Jackson said. "France played awesome."
Suzy Batkovic led the Opals with 17 points and 10 rebounds.
"It's tough when your two best players are fouled out," Batkovic said. "Really disappointed. We didn't play to the best of our ability but it is a long tournament and we have got to keep our heads up.
"What's frustrating is that we can play a lot better game than we did. We need to execute better."
Russia joined France atop preliminary Group B with a 69-59 victory over Brazil with Canada beating Britain 73-65 in the other Group B game.
The United States women, four-time defending champions, stretched their Olympic win streak to 35 games by ripping Angola 90-38.
The Americans share the Group A lead with China, an 83-58 winner over Croatia, and Turkey, which beat the Czech Republic 61-57.
The Aussies, runners-up to the United States in the past three Olympics, jumped to their largest lead at 10-2 in the opening moments but the French battled back to be 28-27 ahead at half-time.
"We were playing so badly and were still up by one, so we said to each other that we could beat these girls," Dumerc said.
France stretched the lead to 51-40 before Australia scored the last 12 points of the third quarter to seize the lead entering the fourth quarter.
Australia's Belinda Snell sank a dramatic three-pointer from just inside the mid-court line at the final buzzer to level the game and force over-time.
"We were lucky that shot went in," Snell said. "It gave us another great opportunity. We will look through things and work on a few more things."
But the French shrugged off the shot to dominate in over-time.
"We tried to stay focused," Yacoubou said. "We said to each other, 'Let's not play with the feeling that we've lost.'"