Although studies have reported the modification effect of air pollutants on heat-related health risk, little is known on the modification effect among various particulate matter with different particle size on mortality. We aimed to investigate whether the associations of hot temperatures with daily mortality were modified by different air pollutant levels in Shandong Province, China. Daily data of air pollutants, meteorological factors, and mortality of 1,822 subdistricts in Shandong province from 2013 to 2018 were collected. We used a time-stratified case-crossover model with an interaction term between the cross-basis term for ambient temperature and the linear function of particulate matter ≤1 µm (PM₁), PM_2.5, nitrogen dioxide (NO₂), and ozone to obtain heat-mortality associations during the hot season. Results showed that the cumulative odds ratio of extreme heat on mortality over 0 to 10 days was 3.66 (95% CI: 3.10–4.31). The mortality risk during hot seasons was stronger at high air pollutant levels. The modification effect of particulate matters on heat-related mortality decreased by its aerodynamic diameter. Females and older adults over 75 years were more vulnerable to the modification effect of air pollutants, and significant differences were detected in the association between temperatures and mortality stratified by PM₁ and PM_2.5. Higher heat-related mortality risks were observed at high NO₂ levels, especially for cardiorespiratory disease. The findings suggest that more consideration should be given to the combined effect of very fine particles and NO₂ with ambient heat when developing healthcare strategies, and women and older adults should be given priority in health-related settings.