New heteroleptic oxovanadium(V) chloro oximato complexes of the type [VO{Cl} 3-n {ON=C(CH 3 )(Ar)} n ] (where Ar = C 4 H 3 O-2, C 4 H 3 S-2, C 5 H 4 N-2 and n = 1 or 2) have been synthesized in excellent yields by the reaction of VOCl 3 with the sodium salts of corresponding internally functionallized oximes in refluxing anhydrous benzene. The complexes are characterized by elemental analyses and spectroscopic techniques (FT-IR, 1 H-, 1 3C{ 1 H}-and 51 V-NMR). FAB mass spectral analysis of one of the derivatives, [VOCl{ON=C(CH 3 )C 4 H 3 S} 2 ] indicates the monomeric nature of the complex. 51 V-NMR spectral studies of these complexes suggest tetra-coordination around the vanadium atom in solution. However, the single crystal X-ray diffraction study of a redistribution product [VOCl{ON=C(CH 3 )(C 4 H 3 S-2)} 2 ] AE CH 3 OH obtained on recrystallization of [VOCl 2 {ON=C(CH 3 )(C 4 H 3 S-2)}] from a methanol-hexane mixture shows the vanadium(V) atom is hepta-coordinated with distorted pentagonal bipyramidal geometry. The oxo-atom occupies the axial position while the weakly coordinated CH 3 OH group is trans to the V=O atom. The two oximato ligands in the approximate pentagonal plane are bonded to the central vanadium atom in dihapto (g 2 -N, O) manner with the formation of three-membered rings. The V-Cl bond occupies the fifth position in the approximate plane.