Catalytic tests for ethanol conversion were performed on vanadium and molybdenum oxides with different oxidation states. We found for the first time that equivalent amounts of ethane and acetaldehyde were formed catalytically over V2O3 and MoO2. No influence of the reaction temperature was observed on the selectivity to ethane and acetaldehyde in the range of 533–653 K over V2O3 and MoO2. The reactions of methanol, 1-propanol, and 2-propanol also produced the corresponding alkanes and aldehydes in a 1:1 ratio. A reaction scheme for the formation of ethane and acetaldehyde from ethanol is proposed in which a hydrogen transfer reaction occurs between two ethanol molecules adsorbed on the adjacent metal cation–oxygen anion pair sites to form ethane, acetaldehyde, and water in one step.