Organic nitrogen aerosols are complex mixtures and important compositions in ambient fine particulate matters (PM2.5), yet their sources and spatiotemporal patterns are not well understood particularly in regions influenced by intensive human activities. In this study, filter‐based ambient PM2.5 samples at four stations (one urban, two rural, plus one urban roadside) and PM samples from combustion sources (vehicle exhaust, ship emission, and biomass burning) were collected in the coastal megacity Guangzhou, south China, for determining water soluble organic nitrogen (WSON) along with other organic and inorganic species. The annual average WSON concentrations, as well as the ratios of WSON to water soluble total nitrogen, were all significantly higher at rural sites than urban sites. Average WSON concentrations at the four sites during the wet season were quite near each other, ranging from 0.41 to 0.49 μg/m3; however, they became 2 times higher at the rural sites than at the urban sites during the dry season. Five major sources for WSON were identified through positive matrix factorization analysis. Vehicle emission (29.3%), biomass burning (22.8%), and secondary formation (20.2%) were three dominant sources of WSON at the urban station, while vehicle emission (45.4%) and dust (28.6%) were two dominant sources at the urban roadside station. At the two rural sites biomass burning (51.1% and 34.1%, respectively) and secondary formation (17.8% and 30.5%, respectively) were dominant sources of WSON. Ship emission contributed 8–12% of WSON at the four sites. Natural vegetation seemed to have very minor contribution to WSON.