Polycyclic aromatic hydrocarbons (PAHs) comprise a group of compounds resulting from the incomplete combustion of organic matter. Firefighters engaged in fire suppression are highly exposed to PAHs. This study centered on evaluating the exposure levels and health risks of PAHs in South Korean firefighters involved in firefighting activities. The concentrations of 10 PAH metabolites in the urine of firefighters were measured immediately after, and two weeks post their engagement in extinguishing a large tire factory fire. The levels of OH-PAHs in urine samples immediately after fire suppression were elevated by a factor of 1.01–1.84 compared to urine samples from non-exposed period. The median concentration of total PAH metabolites (OH-PAHs) was higher in urine samples immediately after fire suppression (5910 ng/g creatinine) than in urine samples from non-exposed periods (5020 ng/g creatinine). However, the ∑OH-PAH levels in firefighters’ urine were related to personal habits such as smoking. The concentrations of all individual OH-PAHs in the urine samples of nonsmokers exhibited a substantial increase, ranging from 1.37 to 2.3 times, clearly demonstrating that firefighting activities were a substantial source of PAH exposure. The calculated values associated with the health risks stemming from exposure to PAHs, including carcinogenic risk, total estimated daily intake (TEDI), and hazard quotients/index (HQs/HI), all fell within acceptable limits, indicating negligible risk. However, the HQ/HI values and TEDI for individual and total PAH exposures, except those for naphthalene, were 1.36–2.00 times higher in firefighters' samples taken after firefighting operations compared to those during regular duty. This underscores the need for more comprehensive investigations to comprehend the singular impact of firefighting activities due to the diverse sources of PAH emissions in the environment.