Heat waves and air pollution extremes exert compounding effects on human health and food security and may worsen under future climate change. On the basis of reconstructed daily O ₃ levels in China and meteorological reanalysis, we found that the interannual variability of the frequency of summertime co-occurrence of heat wave and O ₃ pollution in China is regulated mainly by a combination of springtime warming in the western Pacific Ocean, western Indian Ocean, and Ross Sea. These sea surface temperature anomalies impose influences on precipitation, radiation, etc., to modulate the co-occurrence, which were also confirmed with coupled chemistry–climate numerical experiments. We thus built a multivariable regression model to predict co-occurrence a season in advance, and correlation coefficient could reach 0.81 ( P < 0.01) for the North China Plain. Our results provide useful information for the government to take actions in advance to mitigate damage from these synergistic costressors.