A series of new VO(IV) complexes with two new tetradentate Schiff base of 4,4'-(2,2-dimethylpropane-1,3-diyl)-bis(azan-1-yl-1-yldene)dipent-2-en-2-ol) [H(2)L(1)] and 3,3'-(2,2-dimethylpropane-1,3-diyl)azan-1-yl-1-ylidene)-bis(1-phenylbut-1-en-1-ol) [H(2)L(2)] (which have been derived from 2,2-dimethyl-1,3-diaminopropan, and diketones of acetylacetone and benzoylacetone) were synthesized and characterized by (1)H NMR, (13)C NMR, FT-IR, mass and UV-Vis spectrophotometry. The electrochemical properties of the vanadyl complexes were investigated by means of cyclic voltammetry. The oxidation potentials are increased by increasing the electron-withdrawing properties of functional groups of the Schiff base ligands according to the trend of Me