Mixed ligand, monooxovanadium(V) complexes of Schiff bases with catechol, p-tertbutylcatechol or pyrogallol have been synthesized and characterized by various spectral techniques, such as FTIR, UV-vis, 51V NMR and electrochemistry. All of these complexes exhibited a six coordinated VO3+ center. The stability and the conversion of these complexes to pentacoordinated VO+2 species with the loss of a bidentate catecholate ligand in DMSO were demonstrated using absorption, 51V NMR and electrochemical studies. 51V NMR studies further suggested the formation of two possible isomers in the case of p-tertbutylcatechol and pyrogallol complexes of VO3+. Electrochemistry of these complexes showed one reversible V(V)/V(IV) couple and another irreversible V(IV)/V(III) response. The mixed ligand, VO3+ complexes are more resistant to reduction as compared to the corresponding tris catecholate complexes. Copyright © 1996 Elsevier Science Ltd.