The thermal degradation of PVC resin was examined by the thermogravimetric analysis (TGA). The pyrolysis volatile products were analyzed by Fourier transform infrared spectrometer synchronized with TG test (TG-FTIR). Based on the TG results, the kinetics of thermal degradation was studied by Friedman method. The pyrolysis mechanism was discussed also. The results indicate that the pyrolysis process of PVC can be divided into two main stages: 220°C - 380°C and 380°C - 560°C. By the calculation of mass conservation and TG-FTIR results, it can be supposed that not only HCl, but also some unsubstituted aromatics such as benzene were released during the first stage. The comparison of activation energy shows that the second stage exhibited higher activation energy than the first stage. Two activation energy values in the first stage confirm that there arose two reactions in the first stage.