Poly(3,4-ethylenedioxythiophene) (PEDOT) film was prepared on glassy carbon electrode from 0.1 M LiClO 4 aqueous solution containing 3,4-ethylenedioxythiophene (EDOT) monomer and hydroxypropyl-b-cyclodextrin (HP-b-CD), by multiple scan cyclic voltammetry. The effect of oxidation potentials on electropolymerization of EDOT was examined by chronoamperometry and cyclic voltammetric techniques. The results of potentiostatic experiments show that optimum potential range to obtain compact stable film was 0.9 to 1.05 V (vs. Ag/AgCl). At higher positive potential, i.e. above 1.05 V, polymer growth was hindered by passivation effect. The PEDOT film exhibited a strong absorption at 550 nm in the UV-vis region and also a multicolor electrochromism in different buffer solutions (sky blue-purple red). Cyclic voltammetric features of PEDOT-coated electrode in pure supporting electrolyte suggested that charge transfer of the film resembles that of surface-confined redox species. Finally, the electrocatalytic behavior of PEDOT-modified electrode was tested towards oxidation of sulfur oxoanions and nitrite using cyclic voltammetry.