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The electrochemical oxidation of 3,4-ethylenedioxythiophene (EDOT) on platinum is studied in electrolyte solutions containing hydroxypropyl-β-cyclodextrin (HP-β-CD). HP-β-CD is found to increase the solubility of EDOT up to a concentration of 0.026 M in aqueous solutions. Addition of HP-β-CD (0.1 M) produces a slight red shift of the EDOT main absorption band from 254.9 to 257.7 nm and an increase of the HP-β-CD concentration decreases the absorption coefficient, ε_max to 6150 l mol⁻¹ cm⁻¹ in the UV–vis region, indicating complex formation. The cyclic voltammetric response of EDOT in 0.1 M aqueous LiClO₄ solutions consists of an ill-defined wave (P₁) and an adsorption peak (P₂). Contrary to the case of oxidation in acetonitrile medium, a post-peak is observed in the voltammograms of EDOT electro-oxidation in aqueous LiClO₄ solutions due to the adsorption of the oxidized EDOT species. A gradual …