Demi Vollering took control of La Vuelta Femenina with a statement victory on stage five ahead of the world road champion, Annemiek van Vleuten.

Vollering (SD-Worx) was able to hold off her compatriot on the uphill finish to stage five at Mirador de Peñas Llanas. The 26-year-old, who dominated this year’s spring Classics, takes the red jersey and a five-second lead over Movistar’s Van Vleuten.

The overnight leader, Marianne Vos, was left behind on the category one climb of Puerto de Navafria, midway through the 129km stage from La Cabrera. An initial group of 25 riders went clear, building a lead of three minutes over a group including Vos and Lizzie Deignan.

Among those riders were Élise Chabbey (Canyon-SRAM), who tightened her grip on the queen of the mountains jersey, and Deignan’s Trek-Segafredo team leader, Gaia Realini (Trek-Segafredo). Vollering was supported well by Niamh Fisher-Black until a crash with Ane Santesteban (Jayco-AlUla) led to the New Zealander being cut adrift.

Movistar did their best to try to cut the gap to the leaders and get Liane Lippert back into the mix but, although they got within 30 seconds by the foot of the final climb, the gap grew again. The leading group began to dramatically drop riders, until only Vollering, Van Vleuten and Ricarda Bauernfeind (Canyon-SRAM) remained.

Vollering set the pace before Van Vleuten tried a late attack with 300m to go, but her rival countered to pull clear, claiming victory and the red jersey, with Bauernfeind third. Vos ended the stage more than two minutes down, with Riejanne Markus now Jumbo Visma’s GC leader, 12 seconds behind Vollering.

Demi Vollering leads Annemiek van Vleuten on the final climb to Mirador de Peñas Llanas. Photograph: Dario Belingheri/Getty Images

“Today was a hard day,” Vollering said. “I was really keen to win this [stage] for Niamh. I know I can keep a hard pace for a long time, and I hoped to drop as many as possible. In the end, we were still three. Annemiek tried to go [past] me, and I was like: ‘OK, now is the time to give it my all.’

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“At first, I thought: ‘Maybe this is maybe a bit too early, it’s still a long way,’ but in the end, it was enough.”

The contenders now face two more days in the mountains, starting with two categorised climbs on Saturday’s sixth stage from Castro-Urdiales to Laredo.