Supported perovskite-type catalyst La2AlCoO6–CuCl2–γ-Al2O3 was synthesized by impregnation–sol–gel–mechanical-mixing methods and characterized by means of XRD, BET, H2-TPR, XPS, O2-TPD and TG-DSC techniques. It is found that there is a strong interaction between La2AlCoO6 and CuCl2. The catalyst La2AlCoO6–CuCl2–γ-Al2O3 reduces the reduction activation energy of Cu2+→Cu+ and increases the amount of surface adsorbed oxygen species, which are advantageous to the transition of redox group Cu2+/Cu+, therefore promote the catalytic performance. The catalyst La2AlCoO6–CuCl2–γ-Al2O3 shows a superior catalytic activity for ethane oxychlorination with the C2H6 conversion of 100% and the C2H3Cl selectivity to 43.8%.