This paper focused on the dechlorination of polyvinyl chloride (PVC), a plastic which is widely used in the human life and thereby is leading to serious "white pollution", via vapor treatment process to recycle PVC wastes. In the process, HCl emitted was captured into water solution to avoid hazardous gas pollution and corruption, and remaining polymers free of chlorine could be thermally degraded for further energy recovery. Optimal conditions for the dechlorination of PVC using vapor treatment was investigated, and economic feasibility of this method was also analyzed based on the experimental data. The results showed that the efficiency of dechlorination increased as the temperature increased from 200°C to 250°C, and the rate of dechlorination up to 100% was obtained at the temperature near 250°C. Meanwhile, about 12% of total organic carbon was detected in water solution, which indicated that PVC was slightly degraded in this process. The main products in solution were identified to be acetone, benzene and toluene. In addition, the effects of alkali catalysis on dechlorination were also studied in this paper, and it showed that alkali could not improve the efficiency of the dechlorination of PVC.