Antonia Niedermaier became the virtual leader, attacking with 80km to go, with Elisa Longo Borghini and Niamh Fisher-Black joining her to form a breakaway group.
But Vollering then dropped Van der Breggen with 39km remaining on the Colletta di Brondello, the final climb of the race, and reached the lead group 28km from the finish.
The FDJ-Suez rider did not challenge for the stage win in the sprint finish having already secured the maglia rosa (pink jersey) so Longo Borghini, who won the past two Giros, edged out New Zealand’s Fisher-Black for the Italian’s first stage win of this year’s race.
Vollering finished 30 seconds ahead of Niedermaier in the overall standings, with Van der Breggen a further minute behind, to add the Giro to her La Vuelta Femenina wins of 2024 and 2025, and her Tour de France triumph in 2023.
“I gave it my all on the final climb – it was the time trial of my life,” said Vollering.
“I had to be ready to take risks, even if it meant losing everything. I did it, we did it. I can hardly believe it.”
