Ortho-toluidine is a carcinogen aromatic amine. It is in part eliminated as unchanged form and its urine determination allows biologic monitoriing of occupational exposure. We propose a new method simple and fast in gas chromatography mass spectrometry. In the Nord-Pas-de-Calais region, a company initiated destruction and depollution of an old industrialsite.The GS-MS method permits exposition evaluation of workers employed in demolition of a liquid SO2 plant polluted with ortho-toluidine. This plant has been stopped twenty years ago. These results are compared with results of workers without any exposure in the same company. A 5 mL urine sample spiked with internal standard (ortho-toluidine D9) is extracted with hexane. Derivatisation is achieved with anhydrous pentafluoropropionic acid during 30 min at 60 degrees C. Chromatographic separation is performed on a BPX5MS column (25 m x 0.25 mm, 0.25 microm; SGE). Initial column temperature (60 degrees C) is hold 3 min then is raised to 300 degrees C at 25 degrees C/min. Detection is performed with mass spectrometry with negative chemical ionisation with methane. Acquisition is performed in single ion monitoring. Identification ions are 233 ion (m/z) and 213 ion (m/z) with 233 (m/z) used for quantification. Linearity of the method is verified between 0.1 and 100 microg/L. The limit of detection is 0.02 micro/L. Repeatability and intermediate fidelity are satisfactory (CV < 9%). For unexposed workers, urinary concentrations of ortho-toluidine ranged between 0.17 microg/L and 2.46 microg/g creatinine. Urinary concentrations for exposed workers ranged between 26.14 and 462.00 microg/g creatinine and after new action of protection between 2.35 et 20.11 microg/g creatinine. This new GC-MS method is specific and sensitive and allows for urinary determination of ortho-toluidine. Results showed that this method is adapted for biomonitoring as much for unexposed workers to this aromatic amine as for exposed workers.