The pyrolysis of PVC has been conducted in an inert atmosphere and the products distribution was studied. Gas, liquid and tar fractions were separated and analysed by GC-MS and FTIR. A large number of aromatic compounds and alkyl aromatic compounds were found in the liquid fractions. The results showed that the PVC thermal degradation is substantially a two-step process. The first step mainly involves dechlorination of the polymers. The second stage corresponds to the pyrolysis of the polyene sequences formed during the first stage. The residue produced through the pyrolysis were investigated by C-13 high-resolution solid-state NMR. These details revealed by the high-field NMR spectra provide importmant information about the chemical changes in PVC pyrolysis process.