A new centrosymmetric dinuclear oxovanadium(V) complex, [V2O2(μ-O)2L2], was prepared by the reaction of [VO(acac)2] (where acac = acetylacetonate) with the Schiff base ligand 2-bromo-4-chloro-6-((2-(ethylamino)ethylimino)methyl)phenol (HL) in methanol. Crystal and molecular structure of the complex were determined by elemental analysis, infrared and 1H NMR spectra and single-crystal X-ray diffraction. The V···V distance is 3.105(1) Å. The V atoms in the complex are in octahedral coordination, with the phenolate oxygen, imino nitrogen, and amino oxygen of the Schiff base ligand, and one bridging oxo oxygen in the equatorial plane, and with one oxo oxygen and one bridging oxo oxygen in the two axial positions. Thermal stability of the complex was studied.