The oxidative dehydrogenation of ethane has been investigated over Li-, Na- and K-doped La/CaO catalysts at temperatures of 550-650 degrees C. The addition of alkali metals to La/CaO increases the ethylene selectivity. For Li- and Na-doped La/CaO catalysts, the ethane conversion remains almost unaltered. The increase of ethylene selectivity over the two catalysts is believed to be mainly caused by coordinative action of lithium and lanthanum or sodium and lanthanum. However, the Li-doped La/CaO catalyst exhibits stronger coordinative action than the Na-doped La/CaO catalyst. Catalyst characterization reveals that the strong coordinative action of components in Li/La/CaO is probably related to the chemical and crystal structure of the catalyst which is favorable for oxidative dehydrogenation of ethane. The results also show that addition of potassium, being a poor dopant, to La/CaO results in a sharp decrease in catalytic activity.