A study of nonlinear optical properties of ClO4-doped polythiophenes, galvanostatically electrodeposited on ITO glasses, was carried out using second and third harmonic generation measurements. The effect of the oxidation state of the polymeric films was studied by comparing the nonlinear optical response of oxidised and reduced polythiophenes. Reduced polymeric films show higher values of the second and third order susceptibilities and a lower absorbance in respect to the oxidised ones. The morphology of the polythiophene films was studied by scanning electron and atomic force microscopes.