Electrosynthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) films was performed in a micellar aqueous solution containing sodium dodecyl sulfate (SDS) by cyclic voltammetry, chronoamperometry, and chronopotentiometry on a platinum electrode. The electrocatalytic effect of SDS was characterized by a significant decrease of the EDOT oxidation potential (E-p) in the micellar medium relative to 0.1 M LiClO4 acetonitrile as well as aqueous solutions. Linear variation off, with SDS concentration indicated the formation of a pseudocomplex (K-eq = 5.4 x 10(3) M-1). PEDOT films were characterized electrochemically and spectroscopically (UV-visible, X-ray photoelectron spectroscopy, IR, Raman spectra). Regular, well-ordered, and adherent films were obtained in SDS medium. The PEDOT film morphologies investigated by atomic force microscopy suggested the possible presence of columnar structures when the electrosynthesis is performed in the micellar medium.