Hungary's Kristof Rasovszky took the equivalent men's title in a closely fought battle with his main rivals in the waters of Loch Lomond.
Van Rouwendaal, who won her 2016 Olympic gold over 10km, covered the shorter course in 56 minutes and 01.0 seconds after dominating the race.
The 24-year-old finished 16.8 seconds clear of Germany's Leonie Beck (56:17.8), while Italy's Rachele Bruni won bronze in 56:49.7.
Rasovszky was pushed hard by the pacesetting French duo of Axel Reymond and Logan Fontaine before overcoming them in the final stages.
After a thrilling battle over the last 100 metres, the 21-year-old Rasovszky came first in 52:38.9, less than three seconds faster than Reymond (52:41.7) and Fontaine (52:44.4).
"When the two French guys went to the front, I tried to chase after them and save some energy, enough so that I could try to beat them before the finish because they are so fast," said a delighted Rasovszky.
Reymond, the world champion at 25km, surprised himself by winning silver in this relative sprint for him while his compatriot and race favourite Marc-Antoine Olivier, the world 5km champion, could only finish seventh.
(Reporting by Ian Chadband; Editing by Christian Radnedge and Susan Fenton)
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