Abstract: 9 polyester rope samples of different origins and different specifications were identified by the pyrolysis gas chromatography-mass spectrometry(PY-GC/MS). Firstly, through optimization, the experimental conditions were determined:the pyrolysis temperature was 550℃and the pyrolysis time was 6 s, the column temperature was programed from 50℃(1 min) to 250℃(10 min) at a speed of 20℃/min. Under these conditions, the characteristics of polyester pyrolysis products can be displayed. Pyrolysis analysis results showed that there were 13 main cracking products of polyester fiber, and the characteristics of the product were benzoic acid (relative intensity 100%), vinyl benzoate, biphenyl, benzene etc. Although the 9 polyester ropes had the same cracking characteristics, but the individual pyrolysis products and the relative contents of each characteristic product of were different. It can be used as the basis for the analysis and identification of polyester ropes in different specifications and different regions.