Oxidation of molybdenum(II) thiopivalate and thiobenzoate in the presence of γ-picoline or pyridine results in the formation of dinuclear molybdenum(V) complexes of the general formulae [Mo2O2(μ-O)2(μ-SO4)L4] with L = γ-picoline or pyridine and [Mo2O2(μ-O)(μ-S)(μ-SO4)L4] with L = γ-picoline. As determined by X-ray structure analysis, two complexes with γ-picoline differ in their bridging cores: In one complex, two Mo atoms are doubly bridged through two oxygen atoms; in the other, one Mo atom is doubly bridged through oxygen and sulfur atoms. However, they both crystallize together. The product is solvated with γ-picoline and water molecules. Molybdenum atoms exhibit distorted octahedral coordinations. The same complexes were prepared also through direct reactions of [Mo2O3(O2CCH3)4] with thiopivalic and thiobenzoic acid in the presence of γ-picoline or pyridine. The appearance of the oxo-oxygens and sulfido-sulfur as well as sulfato ligand is explained by the molybdenum-catalyzed oxidation of thiocarboxylates.