Poly(vinyl chloride) PVC pyrolysis and hydrolysis are conducted in a fixed bed reactor and in an autoclave, respectively, under different operating conditions such as the temperature and time. The product distribution is studied. For the PVC pyrolysis process, the main gas product is HCl (55% at 340degreesC), there is 9% hydrocarbon gas (C-1-C-5), the liquid product fraction is about 5% (at 340degreesC), and the solid residue fraction is about 31% (at 340degreesC). For the hydrolysis process, the main gas product is HCl (55.8% at 240degreesC) and the solid residue is about 49.6% (at 240degreesC). The pyrolysis liquid product is analyzed by using gas chromatography with magic-angle spinning. Aromatic hydrocarbons are the main class (90%), of which the major part is benzene (33%). The residue produced through pyrolysis and hydrolysis is investigated by high-resolution solid-state C-13-NMR. These details revealed by the high-field NMR spectra provide important information about the chemical changes in the PVC pyrolysis and hydrolysis process. The mechanism of PVC hydrolysis dechlorination is also discussed. (C) 2003 Wiley Periodicals, Inc.