The oxidative pyrolysis reaction of PVC was studied to investigate effect of adding CuO at various reaction temperature, flow rate, sample ratio. On TGA study according to adding CuO, the evolution of HCl from degraded PVC was decreased by 40% and 45% in oxidative pyrolysis reaction, respectively. On reactor experiment, the evolution of HCl from degraded PVC by adding CuO was decreased over 500℃ reaction temperature, but have no out standing trend in reaction temperature over 500℃ and flow rate. However, according to increasing added CuO, the evolution of HCl from degraded PVC was decreased by increasing sample ratio. The residue from degraded PVC+CuO was analyzed to detect Cl atom on residue surface with EDS. According to increasing added CuO, the mol fraction of Cl atom was increased.