The SD Worx rider timed her sprint to perfection at the top of the ascent to the Cote de la Fosse aux Loups to beat Denmark's Cecilie Uttrup Ludwig (FDJ Nouvelle Aquitaine Futuroscope) and Dutchwoman Marianne Vos (Jumbo Visma).
Twelve women had an advantage of around one minute at 20 kilometres from the finish, as the favourites stayed quiet in the bunch.
But the breakaway was reined in just a few kilometres in from the foot of the climb as the big pre-race favourites contested the final three-kilometre climb.
The attacks began with Australian Tiffany Cromwell's surge attacking as a foil for teammate Kasia Niewiadoma (Canyon-SRAM) and her big attack. Grace Brown (Team BikeExchange) had been in a late attacking group, but still had the power to make contact with Niewiadoma along with Anna van der Breggen (SD Worx).
There was a brief hiatus in attacks after the steepest section of the climb, allowing a few of the other elite climbers to remake contact, including noted sprinter Marianne Vos (Jumbo-Visma). Vos ended up launching the sprint first on the uphill incline to the line, but Vollering jumped onto her wheel and passed her to win comfortably, with Uttrup Ludwig passing Vos to take second.
“It almost went wrong because Vos was going all the way to the right and I was boxed in a bit. Anna made the speed and forced Marianne to go already. Then I could go in Marianne’s slipstream and come over her,” Vollering said of the finish.
“I was really looking forward to the race this morning, but I was not expecting to win. It was an awesome race and gives me a lot of confidence. And now that I won La Course, I am looking forward to the women’s Tour de France next year.”
World champion Anna van der Breggen, who looked the strongest in the steepest part of the final climb, led out the final few hundred metres and ultimately found herself celebrating her teammate and compatriot's victory.
It was 24-year-old Vollering's second big classic win of the 2021 season after she took out Liege-Bastogne-Liege with another rapid final sprint to the line, also set-up by van der Breggen.
La Course will next year be replaced by the women's Tour de France, a weeklong stage race that will start on July 24 - the same day that the men's race finishes in Paris.