Toluene diisocyanate (TDI) is widely used in the production of flexible polyurethane foams, as well as in the formulation of polyurethane paints and coatings. The commercial material is generally a mixture of 2,4- and 2,6-TDI, the predominant mix being 80% 2,4 and 20% 2,6-TDI. The 2,4-isomer is considerably more reactive than the 2,6-TDI at ambient temperatures due to steric factors involving the positions of the isocyanate groups relative to the ring methyl group. Because of this difference in the reactivities of the isomers, it seemed probable that there might be an increase in the amount of 2,6-TDI offgased relative to the 2,4-isomer. Therfore a relative enrichment of the 2,6-TDI has been found in industrial atmospheres. Toluene diamines, which are metabolites of TDI, in urine have a linear relation with exposure to TDI, so that urianry TDA could be used as a biological index of the exposure to TDI. This study was conducted to investigate the distribution of TDI isomer in industrial atmospheres and to propose proper biological monitoring methods by identifying the relationships between the environmental TDI exposure and concentration of TDA in urine. Concentrations of 2,4-TDI and 2,6-TDI in air were 4.38microgram/m3 and 25.43microgram/m3, respectively. The Threshold Limited Value of 40microgram/m3 was exceeded for the 2,6-TDI in about 46.8% (22samples) of the samples, while the 2,4-TDI was not at all exceeded. The ratio between 2,4-TDI and 2,6-TDI varied in air samples in the range, of 2.4%:97.6%-51.0%:49.0%. There was an enrichment of 2,6-TDI in air relative to the 2,4-TDL Concentrations of 2,4-TDA and 2,6-TDA in urine were 1.31microgram/g creatinine and 4.16microgram/g creatinine, respectively. The ratio between 2, 4-TDA and 2,6-TDA varied in urine samples in the range of 1.4%:98.6%-99.9%:0.1%. There was an enrichment of 2,6-TDA in urine relative to the 2,4-TDA. No relation between the concerations of TDA isomer in urine and concerations of TDI isomer in air was found. Above results of this study, workers were more exposed to the 2,6-TDI relative to the 2,4-TDI in industrial atmospheres. Therefore, the establishment of TLV for 2,6-TDI should be considered. Also, the further studies on biological monitorigs of workers exposed to TDI should be continued.