Two new dimeric oxovanadium(V) complexes, [VO2L1](2) (1) and [VO2L2](2) (2), where L-1 and L-2 are the monoanionic form of 2-{1-[2-(2-hydroxyethylamino)ethylimino]ethyl}phenol (HL1) and 2-[1-(2-ethylaminoethylimino)ethyl]phenol (HL2), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single-crystal X-ray determination. The crystal of complex (1) is orthorhombic: space group Pbca, a = 9.284(1), b = 12.733(2), c = 21.626(3) angstrom, V = 2556.5(7) angstrom(3), Z = 4. The crystal of complex (2) is orthorhombic: space group Pbca, a = 9.618(2), b = 12.416(3), c = 21.370(3) angstrom, V = 2552.0(9) angstrom(3), Z = 4. The V<bold></bold>V distances are 3.138(1) angstrom in complex (1) and 3.141(1) angstrom in complex (2). The V atoms in the complexes are octahedrally coordinated. The antimicrobial activity of the free Schiff bases and the complexes were studied. The complexes have potential activities against Staphylococcus aureus, Escherichia coli, and Candida albicans. Supplemental materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.