A pyrolysis gas-chromatographic method (Py-GC) was utilized for the identification as well as the content measurement of textile materials. Py-GC was applied to natural cotton fiber, synthetic polyester fiber, and their blended fabrics. The characteristic peaks originated from thermally decomposed products were observed, and the area of peak increased with the content of polyester. The products of pyrolized polyester were identified as benzoic acid terephthalic acid, and vinyl benzoic acid, which were characterized by mass spectrometry. This analytic method offered a quantitative means to identify the content of cotton and polyester.