Complementary techniques including laser flash photolysis have been used to investigate the mechanism of decatungstate photocatalyzed oxygenation of methanol in acetonitrile. A particular attention has been directed to determine the most important chemical and photophysical kinetic parameters of this peculiar reaction. Under continuous photolysis, kinetics of both oxygen consumption and hydrogen peroxide formation has been followed in a closed system. The reaction was stopped when a conversion of less than 10% in oxygen-saturated solutions was reached. Our work enlightens the following findings: (i) as expected on the basis of a hydrogen-atom-abstraction mechanism and relative C-H bond dissociation energy, the reaction constant rate of reactive species wO with methanol is the weakest of all alcohols already studied, (ii) the methanol decatungstate photocatalyzed oxygenation in acetonitrile satisfies the photostationary state conditions only up to [CH₃OH]∼2.5M, (iii) the role of peroxyl radical is crucial since it not only leads to the resulting products, but it also oxidizes the reduced form of decatungstate H⁺W₁₀O₃₂⁵⁻ to regenerate the catalyst, thus closing the catalytic cycle, and (iv) progressive establishment of anaerobic conditions results in both ending of the substrate conversion and the decay of hydrogen peroxide. Hence, these findings offer new insights into the nature of the rate-determining step in the photocatalytic cycle.