The electrochemical properties of vanadyl(IV) derivatives, namely salen Schiff base complexes of the type [VO(Salen)] (5- BrSalen, 5-NO2Salen, 5-MeOSalen, salpn (bis(salicylaldehyde)-1,3-propanediamine, 5-BrSalpn, 5-NO2Salpn, 5-MeOSalpn, Me2Salen, Salophen, 5-BrSalophen, and 5-MeOSalophen) were investigated. The equatorial Schiff base ligands affect the oxidation potentials via interaction with the d-orbitals of the vanadyl metal ion. The cathodic peak potential (Epc) becomes less negative according to the sequence MeO- < H- < Br- < NO2-.