Polycyclic aromatic hydrocarbons (PAHs) can be transformed into more toxic species in the atmosphere, but field evidence for their transformation remains rare. Here, polycyclic aromatic compounds (PACs), including PAHs and their nitrated and oxygenated derivatives (NPAHs and OPAHs), in fine particulate matter (PM2.5) were measured in the seasons at multiple locations in a megacity (Guangzhou, China). Molecular diagnostic ratios (MDRs), meteorological factors, and atmospheric oxidant measurements were employed to understand the atmospheric behaviors of PM2.5-bound PACs. The results indicated that similarities/differences in the short-term variations of PAC concentrations between the locations depended on their sources and seasons. The temporal trends in MDRs were more distinct than those in concentrations among the locations. Meteorological factors affected PAC concentrations through a similar pathway (demodulating loadings on PM). Their influence on the ratios can be explained by compounds’ atmospheric half-life, vapor pressure, or particle-size distribution. Temperature was the most powerful factor for both the concentrations and MDRs. Relative humidity was minor, but its positive influence on the reaction to OH radicals was appreciable. The dependence on PM2.5 concentrations suggests that PM plays a more significant role in the sorption or formation of N/OPAHs than in their parent compounds. The OH radical-initiated reaction is the major formation mechanism of N/OPAHs throughout the year, but substantial reactions to NO3 radical in autumn were observed due to high ozone levels. Multiple linear regression revealed that parent PAHs, NO2, and/or O3 are significant contributing factors to the secondary formation of N/OPAHs. Partial least squares-discriminant analysis showed the distinguishing characteristics of summer and autumn PM2.5-bound PACs. This study provides field evidence for the gaseous and heterogeneous reactions of PAHs.