Theory predicts that predators are more vulnerable to increasing temperature than prey. Despite huge variations in the magnitude and duration of thermally-extreme episodes in nature, most empirical studies on predator–prey interactions consider conditions induced by a climatic shift in mean temperature. We asked whether the increased vulnerability of predators holds under daily thermal extremes occurring during heat waves, using dragonfly nymphs and newt larvae as the predator–prey model system. Direct exposure of predator to prey in heated and non-heated aquaria under semi-natural conditions revealed that predator movements increased with rising temperature, whereas prey activity decreased. In contrast to the theory of predator–prey space use, the spatial co-occurrence of predator and prey individuals increased with temperature, while predation rates diminished. We conclude that daily thermal extremes affect trophic interactions in the same way, i.e. through the increased vulnerability of predators, as do long-term shifts in mean environmental temperature. Our results highlight the importance of behavioral studies for understanding mechanisms mediating the effect of extreme thermal events on species interactions.