The chemical reactivity, contribution of emission sources, and risk assessment of volatile organic compounds (VOCs) in the atmosphere of the Seoul metropolitan area (SMA) were analyzed. Datasets collected from 6 photochemical assessment monitoring stations (PAMS) of SMA from 2018 to 2021 were used. Alkenes and aromatics contributed significantly to ozone formation relative to the emission concentrations, and aromatics accounted for most of the secondary organic aerosols (SOA) formation in the SMA. The contributions of ozone and SOA formation were found to be notably higher at measurement stations in residential areas such as Guwol (GW) and Sosabon (SS) compared to other measurement stations. From the results of an emission source analysis, it was confirmed that anthropogenic sources such as combustion sources, vehicle exhaust, fuel evaporation, and solvent use had a significant effect at all measurement stations. Assessing the health risk, non-carcinogenic compounds were at acceptable level at all measurement stations. On the other hand, carcinogenic compounds were approaching risk level (10−4), thereby demanding immediate attention. The level of exposure to carcinogenic compounds increased by age group, and male was more vulnerable than female. It was found that SS had the highest level of exposure to carcinogens in the atmosphere of the population ages 60 or older. The health threat of the SMA population is expected due to direct exposure from inhalation of ambient toxic compounds and indirect exposure from ozone and PM2.5 formations through oxidation of VOCs. This study emphasizes the importance of addressing specific emission sources within the metropolitan area and developing comprehensive regional strategies to mitigate VOCs.