Supported perovskite promoted catalysts La2NiMnO6–CuCl2/γ-Al2O3 and La1.7K0.3NiMnO6–CuCl2/γ-Al2O3 were prepared by mechanical mixing method, and characterized by XRD, H2-TPR, XRF, XPS and magnetization techniques. The catalyst doped with potassium La1.7K0.3NiMnO6–CuCl2/γ-Al2O3 possesses a large amount of Mn4+ and surface-adsorbed oxygen species, which accelerate the oxidation of Cu+ by a circular reaction and increase the release of Cl2, and therefore promote the conversion of C2H6 and the selectivity to C2H3Cl. The catalyst La1.7K0.3NiMnO6–CuCl2/γ-Al2O3 shows better catalytic activity for ethane oxychlorination with the C2H6 conversion of 100% and the C2H3Cl selectivity to 59.4%. The total selectivity to C2H4 and C2H3Cl maintains over 81% in 95 h. This study points out a potential way to develop more active perovskite-type oxide catalysts for ethane oxychlorination.