A simple and sensitive gas chromatography (GC) headspace method was developed for the determination of benzene in blood and urine. 1.0 ml of venous blood or urine sample in a headspace vial containing chlorobenzene as an internal standard was incubated at 60 degrees C for 30 min and 0.5 ml headspace gas was used for GC analysis. Unmetabolized benzene in blood or urine was detected at 2.5 min using a silicone gum capillary column and a photoionization detector. The proposed method appears to be more sensitive and reliable than other existing methods, with recovery and reproducibility generally over 90% and a detection limit of 0.64 and 0.51 nmol/l for blood and urinary benzene, respectively. The proposed method was validated with blood and urine samples collected from 25 nonsmokers and 50 smokers. The blood and urine concentrations of benzene in nonsmokers were significantly lower (P < 0.001) than those in smokers: the mean concentrations for blood and urinary benzene, respectively, were 1.42 and 4.21 nmol/l for nonsmokers and 1.49 and 5.19 nmol/l for smokers. A significant correlation (r = 0.61, P < 0.001) was also found between benzene in blood and benzene in urine. These findings suggest that benzene in urine as well as benzene in blood can be used for the biological monitoring of low levels of benzene exposure. Although there was a close correlation between benzene in blood and benzene in urine, no correlation was found between benzene in blood or benzene in urine and the number of cigarettes smoked.