This study assesses the health effects associated with the chemical species of ambient particulate matter (PM) with an aerodynamic diameter ≤2.5 μm (PM2.5) in Seoul, focusing on identifying key chemical constituents and their sources. We employed two approaches to estimate health risks: (1) evaluating carcinogenic and noncarcinogenic risks using IRIS (Integrated Risk Information System) data from the US EPA (Environmental Protection Agency), and (2) quantifying the generation of hydroxyl radicals (·OH) following exposure to PM2.5 in surrogate lung fluid (SLF). Our results show a significant impact on human health from certain elements (Cr, Ni, As, and Cd) and polycyclic aromatic hydrocarbons (PAHs) (DaeP, DahA, and BaP for carcinogenic risks; BaP and BeP for noncarcinogenic risks). Notably, Cr and BaP, which are influential in both risk assessment and ·OH generation, highlight their significant roles in human health impacts. However, other components (e.g., CPP, BaP, BghiP, BaA, CHR, PYR, FLT, Ca, Mg, and Cu), though contributors to ·OH generation, were not included in the EPA's health risk assessment, suggesting a need for a broader PM2.5 compositional analysis to more accurately determine exposure concentrations and assess inhalation risks. These components predominantly originate from anthropogenic sources, such as combustion, vehicles, and industrial activities, underscoring the significant health implications of the pollutants emitted from these sources. The study concluded that focusing solely on the mass reduction of PM2.5 may not suffice; a dual approach that reduces both mass concentration and chemical-specific health risks is imperative for effective public health protection.