Accumulating evidence linked extreme temperature events (ETEs) and fine particulate matter (PM 2.5 ) to cardiometabolic multimorbidity (CMM); however, it remained unknown if and how ETEs and PM 2.5 interact to trigger CMM occurrence. Merging four Chinese national cohorts with 64,140 free-CMM adults, we provided strong evidence among ETEs, PM 2.5 exposure, and CMM occurrence. Performing Cox hazards regression models along with additive interaction analyses, we found that the hazards ratio (HRs) of CMM occurrence associated with heatwave and cold spell were 1.006− 1.019 and 1.063−1.091, respectively. Each 10 μg/m 3 increment of PM 2.5 concentration was associated with 17.9% (95% confidence interval: 13.9− 22.0%) increased risk of CMM. Similar adverse effects were also found among PM 2.5 constituents of nitrate, organic matter, sulfate, ammonium, and black carbon. We observed a synergetic interaction of heatwave and PM 2.5 pollution on CMM occurrence with relative excess risk due to the interaction of 0.999 (0.663−1.334). Our study provides novel evidence that both ETEs and PM 2.5 exposure were positively associated with CMM occurrence, and the heatwave interacts synergistically with PM 2.5 to trigger CMM.