The mononuclear oxidovanadium(V) complex [VO(L)(OEt)(EtOH)] (1), where H2L = Salicyloyl hydrazone of diacetyl monooxime, reacts separately with five different reactants viz. pyridine (py), 4-methylpyridine (4mepy), 4,4′bipyridine (4,4′bipy), 8-hydroxyquinoline (Hox) and KOH to yield the mononuclear oxidovanadium complexes [VO(L)(OEt)(py)] (2), and [VO(L)(OEt)(4mepy)] (3), the binuclear complex [VO(L)(OEt)]2(μ-4, 4′bipy) (4), the mononuclear bis chelate complex [VO(L)(ox)] (5) and the water soluble dioxidovanadium salt K[VO2L]·H2O (6) respectively. Complex 5 has been characterized by X-ray crystallography, and crystallizes in the orthorhombic space group Pna21 having a distorted octahedral O4N2 coordination environment. All five complexes are characterized by elemental analysis, various spectroscopic techniques (UV-Vis, IR, NMR and ESI Mass) and cyclic voltammetry. The spectral and electrochemical data of these five complexes are compared with those of the precursor complex. © 2013 Elsevier B.V. All rights reserved.