Atmospheric particulate polycyclic aromatic hydrocarbons (PAHs) have been drawing sustained attention due to their health risk and effects on air pollution. It is essential to determine the main sources and reduce atmospheric levels of PAHs to protect human health. PAHs in PM2.5 have been detected at five sites located in five districts in Shanghai, a modern metropolitan city in China. Spatial and temporal variations of composition profiles and sources of PAHs at each site in each season were investigated. The results showed that atmospheric particulate PAHs level in Shanghai was the lowest in summer and the highest in winter, dominated by high molecular weight (HMW) PAHs. Analysis with a combination of coefficients of Pearson's correlation and coefficient of divergences indicated heterogeneous spatial and temporal distribution for LMW PAHs and homogenous distribution for HMW PAHs. Diagnostic ratios and positive matrix factorization (PMF) model both identified pyrogenic sources as the main contributor of PAHs in Shanghai, with vehicular source contribution of 32–43% to the total PAHs annually and around 20% from biomass burning emissions in urban and urban buildup areas. While in winter, coal combustion and biomass burning could act as two major sources of PAHs in suburban areas, which could contribute to >70% of total PAHs measured in PM2.5 in Shanghai. Display omitted •HMW PAHs were more homogeneously distributed compared to LMW PAHs.•Suburban sites were subjected to higher BaPeq values in winter, suggesting higher health risks.•Vehicle emission was a major source of PAHs (32–43%) in urban and urban buildup areas.•Biomass and coal combustion were major sources in suburban areas in winter.