o-toluidine was polymerized with the incorporation of different amount of titanium dioxide (TiO2) by chemical oxidation method using potassium perdisulphate as oxidizing agent. Comparative studies were carried out with different nanocomposites of varying compositions of TiO2/PoT against poly-o-toluidine (PoT). The resulting poly-o-toluidine – TiO2 nanocomposites (PoTTNCs) were characterized by UV–Vis and FTIR spectral studies. TiO2 has a deep influence in the crystallinity of PoT chains order in nanocomposite structure as observed in the XRD pattern. Electrochemical characterization studies were carried out to compare the improved performance of varied compositions of TiO2/PoT with respect to PoT in different atmospheres.