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FDJ United-Suez rider Vollering came across the line just ahead of Movistar's Reusser, after the pair overcame an initial launch to the line by Poland's Kasia Niewiadoma of Canyon-Sram.
The three riders fought out the latter stages of a demanding 140km race from Macon to Belleville-en-Beaujolais, close to Lyon, in which they pulled away from rivals with about 10km to go on the category two Mont Brouilly climb, which included a 14% gradient in places.
Switzerland's Reusser retains the overall leader's yellow jersey after winning Tuesday's time trial to Dijon, 12 seconds ahead of the Netherlands' Vollering, with Niewiadoma in third, one minute five seconds further behind.
"Today it was really cool race," said Vollering. "The whole team, every single rider was part of it. I enjoy those victories the most, when everybody put their hard work into it, it makes it more special and beautiful.
"I gave it everything to the line. It was a very long sprint and I needed every single metre in the finish straight, but I managed to do it - I am very happy about that."
It's looking increasingly likely this fifth Tour de France Femmes - since its relaunch as a stage race in 2022 - will be decided between these three riders.
Vollering is in the best form, with 11 wins this season, Reusser the most improved and Niewiadoma potentially in the best position to win Friday's much-anticipated climb up to Mont Ventoux.
It was a bitter day for defending champion and home hero Pauline Ferrand-Prevot of Visma-Lease a Bike, who lost more than two and a half minutes midway through the stage after already losing over two minutes to her main general classifiaction rivals in the time trial.
She now sits five minutes down, 17th overall.
Once dominant, Anna van der Breggan of SD Worx-Protime also lost more than two and a half minutes on the stage, as she also dropped out of contention for yellow overall - more than four minutes down.
The Netherlands' Lorena Wiebes remains in the green points jersey with 131 points, while compatriot Puck Pieterse retains the best climber's polka dot jersey despite losing ground on the stage.
Germany's Antonia Neidermaier of Canyon-Sram takes over the white young riders jersey from Spain's Paula Blasi of Team UAE L'Imad.
Riders' clothing checked at women's Tour over bra padding concerns
Previous image Next image Slide 1 of 4 , Marlen Reusser , Reusser retained yellow after finishing second End of image gallery Tour de France Femmes stage five results
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