Ecosystems are projected to face extreme high temperatures more frequently in the near future. Various biotic coping strategies exist to prevent heat stress. Controlled experiments have recently provided evidence for continued transpiration in woody plants during high air temperatures, even when photosynthesis is inhibited. Such a decoupling of photosynthesis and transpiration would represent an effective strategy (‘known as leaf or canopy cooling’) to prevent lethal leaf temperatures. At the ecosystem scale, continued transpiration might dampen the development and propagation of heat extremes despite further desiccating soils. However, at the ecosystem scale, evidence for the occurrence of this decoupling is still limited. Here, we aim to investigate this mechanism using eddy-covariance data of thirteen woody ecosystems located in Australia and a causal graph discovery algorithm. Working at half-hourly time resolution, we find evidence for a decoupling of photosynthesis and transpiration in four ecosystems which can be classified as Mediterranean woodlands. The decoupling occurred at air temperatures above 35°. At the nine other investigated woody sites, we found that vegetation CO$_2$ exchange remained coupled to transpiration at the observed high air temperatures. Ecosystem characteristics suggest that the canopy energy balance plays a crucial role in determining the occurrence of a decoupling. Our results highlight the value of causal-inference approaches for the analysis of complex physiological processes. With regard to projected increasing temperatures and especially extreme events in future climates, further vegetation types might be pushed to threatening canopy temperatures. Our findings suggest that the coupling of leaf-level photosynthesis and stomatal conductance, common in land surface schemes, may need be re-examined when applied to high-temperature events.