The oxidation of methanol over vanadium oxide, unsupported and applied as a monolayer on γ-Al2O3, CeO2, TiO2, and ZrO2, was studied between 100 and 400 °C in a continuous-flow reactor. At temperatures from 150 to about 250 °C two main reactions take place, (a) dehydration of methanol to dimethyl ether and (b) partial oxidation to formaldehyde. A very slight direct oxidation to CO2 proceeds simultaneously. At higher temperatures two further reactions take place, i.e., (c) consecutive oxidation of the ether and/or formaldehyde to CO and (d) consecutive oxidation of CO to CO2. Selectivity to formaldehyde increased with decreasing reducibility of the catalyst, which in turn was a function of the catalyst-support interactions. Since the reducibility of V(V) has been shown to be related to the charge/radius ratio of the cation of the carrier, the selectivity to formaldehyde is also determined by this ratio.