Two new structurally similar dimeric oxovanadium(V) complexes, [VO(MB)(OCH3)]2 (1) and [VO(NB)(OCH3)]2 (2), where MB and NB are the dianionic form of N'-(2-hydroxy-4-methoxybenzylidene)-3-methoxybenzohydrazide (H2MB) and N'-(2-hydroxy-4-methoxybenzylidene)-2-nitrobenzohydrazide (H2- NB), respectively, were prepared and characterized by IR, elemental analyses, and single-crystal X-ray diffraction studies. The crystal of (1) crystallizes in the monoclinic space group P21/c, with a = 13.347(3), b = 7.830(2), c = 20.566(3) Alpha, beta = 123.920(2)degrees, V = 1783.5(7) angstrom 3, and Z = 2. The crystal of (2) crystallizes in the triclinic space group P1, with a = 8.504(2), b = 10.237(2), c = 10.723(2) angstrom, alpha = 71.826(3), beta = 88.659(3), gamma = 70.016(3)degrees, V = 829.9(3) angstrom 3, and Z = 2. The V center dot center dot center dot V distances are 3.353(1) angstrom for (1) and 3.423(1) angstrom for (2). The V atom in each complex is coordinated by ONO donor set of the hydrazone ligand, by one oxo O atom, and by two methoxy O atoms, forming an octahedral coordination.