The occurrence of polycyclic aromatic hydrocarbon (PAH) derivatives in the environment is of growing concern because they exhibit higher toxicity than their parent PAHs. This study evaluated the large-scale occurrence and spatiotemporal distribution of 16 PAHs and 14 oxygenated PAHs (OPAHs) in urban agricultural soils from seven districts of Guangzhou City, China. Linear correlation analysis was conducted to explore the relationship between PAH and OPAH occurrence and a series of parameters. The compositional analysis, principal component analysis, diagnostic ratios, and principal component analysis coupled with a multiple linear regression model were used to identify the sources of PAHs and OPAHs in the soils. The average concentrations of ΣPAHs and ΣOPAHs (59.6 ± 31.1–213 ± 115.5 μg/kg) during the flood season were significantly higher than those during the dry season (42.1 ± 13.3–157.2 ± 98.2 μg/kg), which were due to relatively strong wet deposition during the flood season and weak secondary reactions during the dry season. Linear correlation analysis showed that soil properties, industrial activities, and agricultural activities (r = 0.27–0.96, p < 0.05) were responsible for the spatial distribution of PAHs during the dry season. The PAH distribution was mainly affected by precipitation during the flood season. The concentrations of ΣOPAHs were only related to the soil properties during the dry season because their occurrence was sensitive to secondary reactions, climate and meteorological conditions, and their water solubility. Our results further showed that coal combustion and traffic emissions were the dominant origins of PAHs and OPAHs during both the seasons. Wet deposition and runoff-induced transport also contributed to PAH and OPAH occurrence during the flood season. The results of this study can improve our understanding of the environmental risks posed by PAHs and OPAHs.