Individual effects of elevated ozone (O3) and warming on wheat (Triticum aestivum L.) are well documented, their combined effects remain poorly understood. In the present study, we investigated the combined impacts of elevated O3 (1.5× ambient O3) and rising canopy temperature (+2°C) on the photosynthesis of wheat leaves in an open‐air field experiment. We found that O3‐induced oxidative stress reduced the biochemical capacity and inhibited leaf photosynthesis at the end of the grain‐filling stage. Night‐time warming (NW) increased leaf photosynthesis during the vegetative stage, but whole‐day warming (WW) did not. Both WW and NW accelerated wheat development and decreased photosynthesis at the end of the reproductive stage. Neither elevated O3 nor warming stimulated antioxidant enzymes. Significant interaction between O3 and WW indicated that WW mitigated the adverse effect of O3 on leaf photosynthesis. Compared to NW, WW significantly increased daytime canopy temperature and canopy‐to‐air vapour pressure deficit across O3 treatments. Decreases in leaf water content and increases in grain oxygen isotope discrimination under warming suggested a link of WW‐induced protection against O3 stress in photosynthesis with declines in stomatal O3 uptake rather than increases in the antioxidant capacity. Our results indicate the need to consider the warming‐induced mitigation of O3 stress on leaf photosynthesis when predicting the effects of elevated O3 on crop growth under warmer climate in the future.