The VOCs and metabolites in urine for exposed VOCs were evaluated for firefighters who participated in the actual fire fighting to determine whether firefighters were exposed to hazardous chemicals, which is the basic data on cancer risk of firefighters. When the fire extinguishing time is long, the concentration of benzene, PHEMA, and toluene among VOCs and metabolites in the case of fire suppression, rescue, and fire investigation work, which is estimated that the exposure of hazardous substances generated from the fire site at the time of fire suppression was large, significantly increased. In the case where the number of urination is 2 or less, the concentration of TZCA, toluene, and benzene among VOCs and metabolites was significantly increased compared to the number of urinating more than 2 times. In the concentration of VOCs and metabolites in urine corrected with creatinine, the concentrations of toluene and PHEMA in urine were significantly higher. The concentration of PHEMA in urine was higher in the group who participated in the fire suppression for more than 11 hours (long time) than the group who participated in the fire suppression for a short time.