A series of Li-doped catalysts on zirconia or sulfated zirconia were prepared and investigated in the catalytic reaction of ethane oxidative dehydrogenation into ethylene. It is found that zirconia and sulfated zirconia supports prepared by different methods show varying nature and thus influence the catalytic performance of their supported Li catalysts in this reaction. Li catalysts doped on the sulfated zirconia prepared by a two-step method can exhibit high ethane conversion, selectivity towards ethylene and ethylene yield as well as a stable catalytic performance. The Li precursors also affect the catalytic behavior. LiCl doped on sulfated zirconia can give high ethane conversion and ethylene selectivity. Addition of transitional and lanthanide metal oxides to the LiCl/SZ system significantly improves the activity and yield of ethylene in the oxidative dehydrogenation of ethane. Among the oxides studied, NiO and Nd2O3 demonstrate the best promoting effect in terms of catalytic conversion and ethylene yield.