Solid state complexes of VO2+ were synthesized from methanolic solutions of VOCl2 and sodium salts of the hexoses (D = Glc, D-Fru, D-Gal) and pentoses (D-Xyl, D-Rib). The complexes were characterized by diffuse reflectance, aqueous solution absorbance, CD, FTIR, EPR spectroscopies, CV, and elemental analysis. The complexes were found to be mononuclear with a general formula, Na2[VO(Sacch)2(OH)Cl] and these are different from those reported earlier which were synthesised by a different route. The aqueous solution stability and pH variation studies of these complexes have shown formation of polymeric species as monitored by UV-visible absorption spectroscopy and cyclic voltammetry. All the complexes exhibited enhanced structural alterations of pUC-18 DNA in the presence of hydrogen peroxide, based on in vitro studies.