Abatract. In present study, two new ligands, i.e., N-isonicotinamido-4´-ethyl benzaldimine (INH-ETB) and N-isonicotinamido-2´,4´-dimethyl benzaldimine (INH-DMB) have been synthesized and investigated for their chelating behaviors towards oxovanadium(IV). All the chelates have general composition VOX₂·L (X = Cl, Br, I, NO₃ or NCS; L = INH-ETB or INH-DMB); and VO(ClO₄)_2·2L. The molar conductance values of VOX₂·L (X = Cl^–, Br^–, I^–, NO^3– or NCS^–) suggest the non-electrolytic nature of these chelates, while the perchlorato complexes dissociate in nitrobenzene and behaves as 1:2 electrolytes. The molecular weights determined cryoscopically in nitrobenzene are in broad agreement with conductance data. The magnetic moments of the VO²⁺ chelates were found to be in 1.74-1.80 BM range. Infrared studies reveal that the ligands behave as bidentate with carbonyl-oxygen and azomethine-nitrogen as two coordination sites. The bands due to heterocyclic ring are almost unaffected on complexation precludes the possibility of tertiary nitrogen-coordination in these complexes. In far IR region the bands in 460-350 cm^-1 region are assigned to n(V-O)/n(V-N) modes. In all the oxovanadium(IV) chelates (V=O) stretching vibrations have been observed in the 980-960 cm^-1 region indicating the presence of monomer (V=O) entity in these chelates. The infrared bands indicate that the perchlorato ions are not bonded to the metal ion, thiocyanate is coordinated through N-atom. In nitrato complexes the monodentate nature of NO^3– in these chelates is suggested. In all the VO²⁺ chelates three bands appeared in the 23000-12000 cm-1 region. The bands are assigned to B.G. Scheme. The t.g. curves of VOX₂·(INH-ETB) (X = Cl, Br, NO³ or NCS) do not show the presence of water molecule either in or out of the coordination sphere. The oxide V₂O₅ informed finally at ~ 640 ºC. In all the oxovanadium(IV) complexes, the coordination number of central metal ion is five and may have a similar square pyramidal structure.