Rookie Puck Pieterse wins stage four of women's Tour de France
It was a first ever road race victory for the cross-discipline star Pieterse, at her first Tour de France.
The result lifted the Dutch rider to second overall, and gave her the best young rider's white jersey and the polka dot climb jersey.
Kasia Niewiadoma of Poland was with the Dutch duo as they entered the final kilometre of a race that started at Valkenberg in the Netherlands, and she launched the dash early with the trio hitting 57kmh after a hilly day.
Defending Tour de France champion Vollering then allowed Pieterse to open a small lead before timing her run to the line slightly wrong.
Stage five takes the Tour into France Thursday with Vollering in yellow and Pieterse second overall at 22sec and Niewiadoma third another 12 seconds back.
Olympic road race champion Kristen Faulkner of the United States is fourth at 47sec.
The Tour finishes on Sunday with one of cycling's most challenging climbs up Alpe d'Huez.