The serious fine particle (PM2.5) pollution in China causes millions of premature deaths. Driven by swift economic growth and stringent control policies, air pollutant emissions in China have changed significantly in the last decade, but the change in the source contribution of PM2.5-related health impacts remains unclear. In this study, we develop a multi-pollutant emission inventory in China for 2005–2015, and combine chemical transport modeling, ambient/household exposure evaluation and health impact assessment to quantify the contribution of eight emission sectors to PM2.5 exposure and associated health risk. From 2005 to 2015, the mortality due to PM2.5 from ambient air pollution (AAP) decreases from 1.04 (95% confidence interval, 0.84–1.25) million to 0.87 (0.70–1.04) million. The agricultural sector contributes 25% and 32% to ambient PM2.5-attributed mortality in 2005 and 2015, respectively, representing the largest contributor during this period. The contribution of power plants drops monotonously from 13% to 6%. The percentage contribution of industrial process drops significantly while the contribution of industrial combustion stays the same level. The overall contribution of industry is still as large as 26% in 2015 in spite of strict control measures. For transportation, despite strict emission standards, its contribution increases remarkably due to the rapid growth of vehicle population. When both ambient and household PM2.5 exposures are taken into account, the mortality due to integrated population-weighted exposure to PM2.5 (IPWE) drops from 1.78 (1.46–2.09) million in 2005 to 1.28 (1.05–1.52) million in 2015. Most of the IPWE reduction comes from domestic combustion as a result of urbanization and improved income, whereas this sector remains the largest contributor (58%) to IPWE-related health risk in 2015. Our results suggest that the government should dynamically adjust the air pollution control strategy according to the change in source contributions. Domestic combustion and agriculture should be prioritized considering their predominant contributions to mortality and the lack of effective control policies. More stringent control measures for industry and transportation are necessary since the existing policies have not adequately reduced their health impacts. Electricity production is no longer the top priority of air pollution control policies given its lower health impact compared with that of other sources.