SignificanceExposure to co-occurrence of air pollution and heat extremes is likely to induce amplified damages to both human health and ecosystem. This study identifies the relationship between co-occurrence of heat wave and O3pollution in China and large-scale climate patterns, which offers preseasonal hints. The robustness of the findings is demonstrated with both statistical analysis and numerical coupled experiments. The results could help the government to take actions in advance to mitigate damages.