The oxidation of ethane by oxygen was studied over silica catalysts supporting different amounts of vanadium with and without cesium. Three different catalytic properties of the product selectivity were observed, aldehyde formation, oxidative dehydrogenation (ODH), and combustion, depending upon the vanadium loading amount and the presence or the absence of cesium. A very low loading of vanadium (V:Si=0.02–0.1 at.%) and the addition of Cs (Cs:Si=1 at.%) on silica were found to be important for the formation of aldehyde. Not only acetaldehyde but also acrolein were observed in the aldehyde formation from ethane. On the other hand, catalysts with medium and high vanadium loadings (V:Si=0.5–20 at.%) gave a dehydrogenated product, ethene, when Cs was not added to the catalysts. The addition of cesium to the catalysts with medium and high vanadium loadings changed the catalytic property from ODH to combustion. The different types of vanadyl species were identified by UV–visible and IR measurements in samples with different vanadium loadings. It was estimated that isolated vanadyl species with tetrahedral coordination, which were found mainly on the catalysts with vanadium loading lower than 0.5 at.%, became the active site for the aldehyde formation through the interaction with Cs. As a plausible reaction path giving acrolein from ethane, cesium-catalyzed cross-condensation between acetaldehyde and formaldehyde, formed in the reaction, was proposed. Polymeric vanadyl species with octahedral coordination and vanadium–oxygen clusters with dioxo tetrahedral coordination were detected in the samples with medium (0.5–5.0 at.%) and high (10 and 20 at.%) vanadium loadings, respectively. Both species show the ODH catalytic property without cesium, but they bring about a deep oxidation of ethane if cesium is added to the catalysts.