Van Rouwendaal won with a time of 2hr 03min 34.2sec, with Australian Moesha Johnson taking silver 5.5 seconds behind and Italy's Ginevra Taddeucci claiming bronze.
The race took place on the River Seine with the Eiffel Tower in the background after water pollution levels were deemed sufficiently safe for competition.
Van Rouwendaal, the gold medallist in Rio in 2016 and silver medallist in Tokyo, made her move past Johnson around a pilon coming under the Pont des Invalides bridge.
The 30-year-old Dutchwoman, who was also world champion in Budapest in 2022, never looked back as she powered her way to the finish.
It was a crushing blow for Johnson who had led from the half-way mark onwards and was out front with the top three having broken well clear of the field going into the final lap.
The decision to hold the race on the river produced a glorious spectacle but had caused headaches for organisers.
The triathlon was badly disrupted by poor bacterial readings last week, with all swim training sessions cancelled and the men's individual race postponed by 24 hours until Wednesday.
Training for the 10k race had been cancelled due to the water pollution levels.
