Understanding the factors that drive PM2.5 concentrations in cities with varying population and land areas is crucial for promoting sustainable urban population health. This knowledge is particularly important for countries where air pollution is a significant challenge. Most existing studies have investigated either anthropogenic or environmental factors in isolation, often in limited geographic contexts; however, this study fills this knowledge gap. We employed a multimethodological approach, using both multiple linear regression models and geographically weighted regression (GWR), to assess the combined and individual effects of these factors across different cities in China. The variables considered were urban built-up area, land consumption rate (LCR), population size, population growth rate (PGR), longitude, and latitude. Compared with other studies, this study provides a more comprehensive understanding of PM2.5 drivers. The findings of this study showed that PGR and population size are key factors affecting PM2.5 concentrations in smaller cities. In addition, the extent of urban built-up areas exerts significant influence in medium and large cities. Latitude was found to be a positive predictor for PM2.5 concentrations across all city sizes. Interestingly, the northeast, south, and southwest regions demonstrated lower PM2.5 levels than the central, east, north, and northwest regions. The GWR model underscored the importance of considering spatial heterogeneity in policy interventions. However, this research is not without limitations. For instance, international pollution transfers were not considered. Despite the limitation, this study advances the existing literature by providing an understanding of how both anthropogenic and environmental factors, in conjunction with city scale, shape PM2.5 concentrations. This integrated approach offers invaluable insights for tailoring more effective air pollution management strategies across cities of different sizes and characteristics.