Investigations of the pyrolysis of poly(vinyl chloride) (PVC) in the presence of copper metal (Cu), copper(II) oxide (CuO) and copper(II) chloride (CuCl 2) are of potential importance because of the likelihood of the formation of these copper compounds during the thermal degradation of PVC-coated copper wires, a step in the recovery of copper from waste. The presence of Cu, CuO and CuCl 2 (i) retards the thermal degradation of PVC in air and in nitrogen and (ii) decreases the percentages of volatile products produced at both stages of the decomposition. These effects are greatest for PVC–CuO. The presence of copper, CuO or CuCl 2 in PVC has a major effect on the nature of the gaseous emissions of the thermal decomposition in air and in nitrogen. The concentrations of total chlorine, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons and soot particulates are all affected relative to an equivalent amount of PVC. These changes are greatest for the PVC–CuO system for which total chlorine emissions in air and nitrogen are reduced by 40% in air and 20% in nitrogen, benzene emissions are reduced by greater than 90% in air and nitrogen, other aromatic and chloroaromatic emissions are reduced, and soot particulate emissions are reduced by more than 50% as the concentrations of aliphatic compounds are increased. These changes are consistent with the presence of copper or its compounds permitting more efficient combustion of the carbon content of the PVC and particularly in the case of PVC–CuO with the removal of chlorine during pyrolysis in the inorganic phase.