The thermal decomposition characteristic of waste PVC wires has been studied by using TGA and fixed-bed reactor. The experimental conditions of decomposition temperatures, air flow rates and weight ratio of CaO/PVC were considered in this work. To verify the effectiveness of CaO addition to remove HCl and toxic gases generated from thermal decomposition of PVC wire, the gaseous products obtained from the thermal decomposition of PVC were analyzed by GC/MS(Gas Chromatograph and Mass Spectrometry). To investigate the effect of CaO in thermal decomposition of PVC, liquid products were also analyzed by GC/MS. And the effect of decomposition temperature, air flow rate and CaO/ PVC weight ratio on the yield of liquid, gas and residue fraction have been also studied. From this work, it was found that the removal amount of HCl generated from thermal decomposition of PVC increased with increase of CaO addition.