Electrochemical properties of a series of differently substituted vanadyl salen complexes were investigated using cyclic voltammetry in different solvents. Results obtained show that the salen structure stabilizes the oxidized forms and that the effects of substituents on the oxidation potential correlate with the electronic density of the metal. Also the role of the donicity of the solvent in influencing the redox potentials of the studied complexes has been evidenced. Moreover, the variations of the observed potentials can be qualitatively correlated to the catalytic activity of vanadyl salen derivatives in the oxidation of thioethers.