Hydrothermal treatment (HTT) is able to remove chlorine effectively from polyvinyl chloride (PVC), however, the reaction temperature is critical in practical application. Less energy-intensive hydrothermal dechlorination condition with cupric ion (Cu2+) has been proposed in this study. In particular, Cu2+ was applied in HTT of PVC at temperature ranging from 200 °C to 240 °C. It has been found that the introduction of Cu2+ distinctly accelerated PVC decomposition and dechlorination at 220 °C. When Cu2+ concentration was increased from 0.01 mol/L to 0.20 mol/L, the dechlorination efficiency was significantly improved from 15.46 %–67.89 %. Dramatic dechlorination occurred as residence time was longer than 15 min during HTT. Besides, both elimination and substitution dominated the HTT dechlorinaton. The facilitated dechlorination after the addition of Cu2+ was mainly due to the enhanced dispersion and formation of micropores in hydrochar. On the whole, HTT could be a promising pretreatment technology for copper-containing PVC in electronic wastes to prepared chlorine free hydrochar for combustion or pyrolysis applications, the optimal HTT condition would be 220 °C, 60 min with 0.1 mol/L Cu2+.