The partial photooxidation of methane by nitric oxide selectively led to methanol formation over the V-MCM-41 catalysts under UV irradiation (lambda > 270 nm) at room temperature, while only a complete oxidation of methane could occur in the presence of oxygen. The yield of methanol corresponds with the yield of the photoluminescence of the isolated tetrahedrally coordinated V-oxides species, indicating that the charge transfer excited triplet state of these species are active sites in this photooxidation reaction.