This study investigated the occupational exposure of Korean firefighters to a suite of combustion-related pollutants. Exposure to polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) was assessed by measurement of their levels in serum and metabolites in urine (i.e., monohydroxylated PAHs, OH-PAHs). The mean level of ∑PBDEs in the serum of firefighters (17.1 ng/g lipid weight (lw)) was significantly higher than that of the general population (1.39 ng/g lw) (Mann–Whitney U Test, p < 0.05), which is similar to the ∑PAH levels (1286 ng/g lw for firefighters and 1016 ng/g lw for the general population). Individual OH-PAH levels showed 2.1- to 4.2-fold increases in postfire urine samples compared to the control urine samples, with the mean ∑OH-PAHs being significantly higher in postfire urine samples (22,658 ng/g creatinine) than in the control urine samples (10,253 ng/g creatinine) (Mann–Whitney U test, p < 0.05). It was found that ∑PBDEs correlated with firefighters’ length of service and years dedicated to on-site dispatch, while ∑OH-PAHs was strongly associated with firefighters’ exposure duration, age, length of service, and years dedicated to on-site dispatch. Indeed, the results of the present study indicate that Korean firefighters are prone to elevated risk of exposure to toxic combustion-related pollutants compared with the general population.