It was the world champion that illuminated the racing at the European championships, raced around a 106-kilometre loop around Plouay in France.
Van Vleuten looked to be laying the foundation for teammate Chantal van den Broek-Blaak, when she and her Dutch teammate were away with Kasia Niewiadoma (Poland) and Elisa Longo Borghini (Italy) with the quartet to battle it out for the win.
Van den Broek-Blaak by a fierce Longo Borghini attack, and van Vleuten tried a few of her own to try and escape, but the pair could not drop each other and only succeeded in ditching Niewiadoma.
Coming in to the final kilometres, van Vleuten initially refused to pull through knowing her teammate van den Broek-Blaak, the strongest sprinter of the four riders, was catching up. However, Longo Borghini pulled the leading pair through the final kilometre of the race and into a two-up sprint.
Van Vleuten launched her sprint at the bottom of the uphill drag to the line, and while Longo Borghini tried to sprint as well, it was not enough to catch Van Vleuten at the finish line.
"Thanks to the Dutch squad because we lined up with a dream team," said Van Vleuten, who was making her debut at the European championships. "We had eight super-strong girls and we decided that it was in our advantage to make the race really hard.
"Between myself and Anna van der Breggen, it was both our jobs to make the race super hard to set something up for the other girls. I was so proud to race together with my team and I am so proud to do this together."
If you want to catch more exciting women's racing watch La Course by Le Tour de France LIVE streaming via SBS On Demand from 6pm (AEST) on Saturday August 29, and on SBS from 7.30pm (AEST).