A method based on liquid chromatography (reversed-phase)-electrospray (negative) ionization-tandem triple quadrupole mass spectrometry [LC-ESI(-)-MS-MS], in the multiple reaction monitoring mode, was developed for determination of urinary benzylmercapturic acid (BMA). Isotope dilution through introduction of (13)C(6)-labeled BMA was employed as an internal standard, achieving intra- and interrun precision ranges of 2.32-2.95% and 2.24-4.97%, respectively. The calibration curve obtained with BMA-spiked blank human urine was linear from 0.5-120.0 microg/L; the correlation coefficient of the calibration curve was 0.999. The method limit of quantification was 0.5 microg/L; mean BMA recovery was 97.56%. The analytical method was used to analyze urine samples collected from workers involved in the manufacture of adhesive tape who had been exposed to toluene. The method appears to provide sensitive, specific, and reliable testing for urinary BMA to determine occupational exposure to toluene.