The growth, and reactivity of monolayer V2O5 films supported on TiO2(110) produced via the oxidation of vapor-deposited vanadium were studied using X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Oxidation of vapor-deposited vanadium in 10-7 Torr of O2 at 600 K produced vanadia films that contained primarily V+3, while oxidation in 10-3 Torr at 400 K produced films that contained primarily V+5. The reactivity of the supported vanadia layers for the oxidation of methanol to formaldehyde was studied using TPD. The activity for this reaction was found to be a function of the oxidation state of the vanadium cations in the film.