In China, rural migrant workers (RMWs) are employed in urban workplaces but receive minimal resources and welfare. Their residential energy use mix (REM) and pollutant emission profiles are different from those of traditional urban (URs) and rural residents (RRs). Their migration towards urban areas plays an important role in shaping the magnitudes and spatial patterns of pollutant emissions, ambient PM2.5(fine particulate matter with a diameter smaller than 2.5 $μ$m) concentrations, and associated health impacts in both urban and rural areas. Here we evaluate the impacts of RMW migration on REM pollutant emissions, ambient PM2.5, and subsequent premature deaths across China. At the national scale, RMW migration benefits ambient air quality because RMWs tend to transition to a cleaner REM upon arrival at urban areas—though not as clean as urban residents’. In 2010, RMW migration led to a decrease of 1.5 $μ$g/m3in ambient PM2.5exposure concentrations (Cex) averaged across China and a subsequent decrease of 12,200 (5700 to 16,300, as 90% confidence interval) in premature deaths from exposure to ambient PM2.5. Despite the overall health benefit, large-scale cross-province migration increased megacities’ PM2.5levels by as much as 10 $μ$g/m3due to massive RMW inflows. Model simulations show that upgrading within-city RMWs’ REMs can effectively offset the RMW-induced PM2.5increase in megacities, and that policies that properly navigate migration directions may have potential for balancing the economic growth against ambient air quality deterioration. Our study indicates the urgency of considering air pollution impacts into migration-related policy formation in the context of rapid urbanization in China.