In accordance with the process of this invention, an improved catalyst for molecular oxidation of a hydrocarbon to form the corresponding carboxylic anhydrides is prepared by the steps of (a) forming a catalyst precursor by depositing on titanium dioxide solids in the anatase form a discontinuous monolayer amount of at least one source of a Group VIB metal oxide; (b) calcining the thus-formed catalyst precursor under conditions sufficient to convert the Group VIB metal oxide source into the corresponding group VIB metal oxide; (c) depositing upon amount of at least one vanadium oxide source which is calcining the vanadium-deposited solids under conditions sufficient to convert the vanadium compound into vanadium oxide.