Pooley is the current British road race champion
Britain's Emma Pooley won the Grand Prix de Plouay race - the ninth and final round of the UCI Road World Cup - for the second year in a row.
The Olympic time trial silver medallist finished by one minute and 14 seconds ahead of second-placed Marianne Vos.
Pooley's Cervelo outfit secured the team title.
"It is just amazing, this victory," said Pooley, 27. "I didn't expect that but the course and terrain of western France seems to fit me."
Pooley continued: "We were a group of four riders coming into the final lap.
"As I am not so strong in sprints I tried my luck at the Cote de Kerihuel and attacked but Marianne Vos was still on my wheels on the top.
"So I attacked again at Ty Marrec and this time I was able get away and pushed hard on the final kilometres."
The victory was Pooley's second World Cup win of the season, following her Flèche Wallonne triumph in the spring.
Dutch rider Vos won the overall title, with Pooley finishing eighth and Team GB's Nicole Cooke, from Wales, 10th.
Meanwhile, Team Sky's Greg Henderson won the fourth stage of the Eneco Tour in a sprint finish.
New Zealander Henderson's team-mate Edvald Boasson Hagen took third on the 212km route from St-Lievens-Houtem in Belgium to Roermond in the Netherlands.
"I felt good all day and wanted to show I can sprint a bit," said Henderson.
"I just kept everyone moving forward at the finish and we got into exactly the position we wanted; so much so that Edvald, who is obviously very fast himself, was able to deliver me and get on the podium himself."
Germany's Tony Martin (HTC-Columbia) maintained his overall advantage.