Abstract Ambient fine particulate matter (PM2.5) is one of the most concerning pollutants, characterized by its diverse chemical composition. Although various studies have revealed PM2.5 chemical components, there is limited knowledge on how to reduce PM2.5 concentrations through administrative policies focusing on source management. We compared PM2.5 compositional characteristics and performed source apportionment using the positive matrix factorization in four metropolitan cities (Seoul, Daejeon, Gwangju, and Ulsan) in South Korea from 2014 to 2018. The annual average of PM2.5 concentrations exceeded the annual national ambient air quality standard of 15 μg m−3 in all areas while secondary inorganic aerosols constituted the largest fraction of PM2.5. This implies that secondary formation from gaseous precursors in the atmosphere was the main factor contributing to ambient PM2.5. However, the concentrations of PM2.5 constituents varied significantly across cities, suggesting that PM2.5 is a heterogeneous pollutant considerably influenced by region-specific conditions. In line with the chemical composition, secondary nitrate, secondary sulfate, and mobile-related sources were found to be significant contributors of PM2.5. Additionally, the extent of contribution from each source varied across the study regions. We also evaluated the impacts of policy interventions by comparing the PM2.5 composition and source apportionment before and after the policies for improving air quality. Intensive programs focused on the vehicle sector in Seoul led to a considerable decrease in the concentrations of carbonaceous compounds and mobile-related sources. In addition, strengthened regulations on coal-fired power plants (CFPPs) since 2016 have influenced the contributions of coal combustion sources in two cities adjacent to the west coastal area, where approximately half of the CFPPs of the country are densely distributed. Overall, the study’s findings indicate that region-specific PM2.5 chemical constituents and source contributions should be considered for establishing PM2.5-related policies, considering the high heterogeneity of PM2.5.