Thiodiglycolic acid (TdGA) is the major metabolite of vinyl chloride monomer (VCM) detected in human urine. Although urinary TdGA has been reported to be associated with ambient VCM exposure, the relationship between urinary TdGA and a low level of air VCM is not clear. Questionnaires were administered to 16 polyvinyl chloride manufacturing workers to obtain a detailed history of occupation and lifestyle. For each worker, personal air monitoring for VCM was performed and a time-weighted average for VCM exposure was calculated. The urinary TdGA levels at the end of a work shift, and at the commencement of the next shift, were also assessed for each worker. Urine analysis revealed that TdGA levels at the beginning of the next shift were higher than those at the end of that shift. Workers experiencing a VCM exposure greater than 5 ppm in air revealed a urinary TdGA level significantly greater than those experiencing a VCM exposure of less than 5 ppm (P < 0.05). The best fit of regression for urinary TdGA on air VCM was Y = 1.06 + 0.57X for urine collected at the commencement of the following work shift, where X is the air VCM concentration and Y is the urinary TdGA concentration (r2 = 0.65, P < 0.01). We conclude that the urinary TdGA level is best detected at the commencement of the next shift and that it can be used as an exposure marker for polyvinyl chloride workers when the air VCM level to which they are exposed is greater than 5 ppm.