Biological monitoring of workers exposed to N,N-dimethylformamide (DMF) was carried out by determination of the urinary metabolites, N-methylformamide (MF, mainly from N-hydroxymethylformamide) and N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC), which were derived from two different routes of metabolism of the solvent. The urinary levels of MF increased rapidly at the start of the work shift, and decreased almost to zero within 24 h after the beginning of the last exposure. The highest level was found between the end of the afternoon shift and bedtime. AMCC levels remained constant over the consecutive work days and increased after the cessation of exposure, with the peak concentration being observed at 16-40 h after the cessation of exposure. AMCC levels at the beginning of the next morning shift were closely correlated with personal exposure levels of DMF in air, although the correlation of MF and DMF in air was highest in the urine at the end of the shift. Hence urinary AMCC represents an index of the average exposure during several preceding work days and may indicate the internal dose. By contrast, MF represents an index of daily exposure.