At the 2016 Summer Olympics in Rio de Janeiro, Van Rouwendaal missed the final of the 400 m freestyle, finishing 19th in the heats. She subsequently pulled out of the 800 m freestyle, and later won the gold medal in the 10 km marathon at Fort Copacabana in 1:56:32.1. After 6 km she broke away from the field, and finished 17 seconds ahead of silver medalist Rachele Bruni.