Two dinuclear water-soluble oxovanadium (V) complexes [(L1H)VO(μ-O)]2 (C1) and [(L2H)VO(μ-O)]2 (C2) were prepared from VOSO4 and the corresponding tetradentate Schiff base ligands [N-(2-hydroxyethylamino)ethyl]-5-methoxysalicylaldimine (L1H) and 2-[(2-(2-hydroxyethylamino) ethylimino)methyl] phenol (L2H) in refluxing methanol. Their catalytic performance in the oxidation of olefins was explored in water as green solvent using different oxidant agents. Our results demonstrate the effectiveness and good yield of the catalysts by ensuring its effective reusability. The electrochemical behaviour of oxo-vanadium complexes were investigated using cyclic voltammetry (CV). The results showed that complexes exhibit one-electron transfer coupled with the electrochemical irreversibility of the process (ErCi mechanism) corresponding to the VOIV/VOV. The irreversibility behavior of the complexes was showed with the scan rate growing and deformation of peaks.