Objectives: Firefighters could be exposed to a range of toxic chemicals during firefighting. When tyre burns, various toxic chemicals including volatile organic compounds(VOCs) could be emitted. In this study, the researchers assessed the VOC exposure of firefighters during tyre fire suppression through biomonitoring. Methods: There was a big tyre fire on 12 March 2023. Of the responding firefighters, we recruited 14 participants to collect their urine after firefighting. One week later, researchers collected firefighters’ urine again right after their off-duty period. We analyzed each metabolite of benzene, toluene, xylene, and styrene in urine and compared their exposure level based on sampling time. Results: The detection rate for metabolite of benzene, toluene, styrene, and xylene in urine sampled at each time was 43%-64%, 100%, 86%-100%, and 100%, respectively. Except for the benzene, metabolite levels measured in urine after firefighting were similar to that from off-duty period. However, the median concentration of benzene metabolite in urine sampled after firefighting was three times higher compared to that from off-duty period(34.2 ㎍/g crea. and 10.9 ㎍/g crea., respectively.) The estimated airborne concentration of benzene calculated from metabolite level in urine was 0.16 ppm, which exceeded the recommended exposure level set by the National Institute for Occupational Safety and Health. Conclusions: This study shows that firefighters could be exposed to the high level of VOCs including benzene during their firefighting especially at tyre fire. These results could be used as a valuable data to prove firefighters’ exposure to hazardous chemicals during their duty.