The hydrodechlorination of 1,1,2-trichloroethane (TCEA), which is one of the chlorinated organic wastes produced in the ethylene dichloride process, to vinyl chloride monomer (VCM) was carried out over Ni-Cu/SiO2 catalysts. The effects of added metals from IB group and the Cu content on the performance of the bimetallic catalysts were systematically investigated. Of the screened bimetallic catalysts tested, Ni-Cu/SiO2 catalysts efficiently converted TCEA into VCM in 95% or higher selectivity. Cu in Ni-Cu/SiO2 reduced the metal particle size and weakened the adsorption strength of Ni, and led to low conversion of TCEA and a high VCM selectivity. A series of CO-IR and extended X-ray absorption fine structure (EXAFS) measurements revealed that added Cu had no effect on the electronic structure of Ni and that Cu altered the geometric nature of Ni-Cu/SiO2 catalyst. HCl converted metallic Ni to NiCl2 and Cu to CuCl to modify the crystal structure. Cu played a role in the cooperation with Ni in the hydrodechlorination of TCEA, serving as other than an inert spacer.