FDJ-Suez rider Vollering took the leader’s red jersey with victory in the race’s other mountain stage on Thursday.
“I am very happy that I could win both mountain stages,” said Vollering, who moved to FDJ from SD-Worx this season.
“My team was so strong again, so strong, and we were always in control. I’m really happy about the whole performance with the whole team.”
Van der Breggen, who returned to competing this year after retiring in 2021, started the day second and led for much of the final 10.3km climb in the rain on the 152km route from La Robla to Cotobello.
But she had no answer for Vollering’s explosive attack with around 800 metres to go, also falling behind Reusser.
Vollering has now won three major tour titles in women’s cycling, having won the 2023 Tour de France Femmes to go with her two Vuelta triumphs.
Her second victory of the race also ensured every individual stage was won by a Dutch rider.
After American outfit Lidl-Trek claimed the opening team time trial, Marianne Vos won stages two and six, Van der Breggen won stage four and Femke Gerritse took victory on stage three.
