A novel binuclear oxidovanadium(V) complex [V2O2(μ-O)L2(OEt)2], where L is the deprotonated form of 2,4-dibromo-6-(5-methylamino-[1,3,4]thiadiazol-2-yl)phenol (HL), was prepared by the reaction of 2-(3,5-dibromo-2-hydroxybenzylidene)-N-methylhydrazinecarbothioamide (HL') and VO(acac)2 in ethanol. The ligand L' underwent a cyclization during the coordination, to form a new ligand L. Structure of the complex was characterized by physicochemical methods and single-crystal X-ray determination. Crystal of the complex crystallizes in hexagonal space group R-3, with a = b = 33.302(3) Å, c = 15.308(2) Å, α = β = 90°, γ = 120°, V = 14702(3) Å3, Z = 18, R1 = 0.0823, wR2 = 0.2064, S = 1.011. X-ray analysis indicates that the V atom in the complex is in an octahedral coordination environment, constructed by the phenolate O and thiadiazol N atoms of L, one oxido O atom, one bridging O atom, and one deprotonated ethanol O atom. The distance between the two V atoms is 3.365(1) Å. The complex has an effective catalytic property for the oxidation of several olefins. [ABSTRACT FROM AUTHOR]