The 27-year-old, who won the Tour de France last year, earned her first triumph of the season by winning the race for the first time, lifting her bike in celebration.
Vollering came second in Spain last year but this time triumphed at Valdesqui, north of Madrid, with a dominant performance.
The SD Worx-Protime rider arrived as general classification leader after her stage five win, her first of the season, and never looked like letting it slip out of her grasp in the red jersey.
She edged out compatriot Riejanne Markus and Italy's Elisa Longo Borghini in the overall classification, one minute and 49 seconds and two minutes behind respectively.
Markus finished third behind Evita Muzic, which was enough to take second place overall after Longo Borghini struggled and came in seventh, a minute behind Vollering.
"I'm really happy to win this stage because it's really nice to finish it off like this, we did a really good Vuelta, some podiums and two stage wins, so I think we can be very proud of ourselves," said Vollering.
"It is a good start, I hope I can do some other really nice stage races of course, and I am looking really much forward to the rest of the season."
The women's Vuelta ran as a one day race between its inception in 2015 and 2022, changing to a multi-day event in 2023, won by Dutchwoman Annemiek van Vleuten.
Van Vleuten is the record winner of the event with three triumphs.
