New vanadium oxodiperoxocomplexes Bu4N+[VO(O-2)(2)L-2](-) were synthesized, where L = pyridine(1), 2-methylpyridine (2),4-methylpyridine (3),2-oxymethylpyridine (4). All complexes were characterized by NMR (H-1, V-51) and IR spectroscopy. The oxidation of sulfur organic compounds and diesel fuel desulfurization catalyzed by vanadium peroxocomplexes in bi-phase system was investigated in various solvents. The complexes manifested high catalytic activity and selectivity in oxidation of sulfides.