A new oxovanadium(V) complex, [VOL(OCH3)(CH3OH], where L is N'-(3,5-ditertbutyl-2-hydroxybenzylidene)-4-methoxybenzohydrazide, was prepared and structurally characterized by physicochemical methods and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P2(1)/c, with a = 8.958(1) angstrom, b = 12.479(2), c = 23.289(2) angstrom, beta = 94.032(3)degrees, V = 2597.0(5) angstrom(3), Z = 4, R-1 = 0.0387, and wR(2) = 0.0942. X-ray structural analysis indicates that the benzohydrazone ligand coordinates to the V atom through the phenolate O, imino N, and enolic O atoms. The V atom in the complex is coordinated by one benzohydrazone ligand, one methoxy ligand, one methanol ligand, and one oxo O atom, forming an octahedral coordination. The crystal structure of the complex is stabilized by hydrogen bonds. The complex is an effective catalyst for sulfoxidation.