Electropolymerization of poly-(o-phenylenediamine) (PoPD) film was performed in a micellar aqueous solution containing sodium dodecyl benzene sulfate (SDBS) by cyclic voltammetry at conducting glass electrode. The experimental results showed that the anionic micelle, i.e., SDBS, can greatly catalyze the electropolymerization reaction of oPD and reduce its oxidation potential from 0.97 to 0.74 V (vs. saturated calomel electrode). In the anionic micellar media, the local concentration of o-phenylenediamine (oPD) on the surface of electrode may be increased, and the oPD cation radicals are more stabilized in the hydrophobic microcircumstance of micelle, which is available to avoid hydrolysis degradation of PoPD and enhance the stability of the PoPD film. The spectroscopy and morphology of the films were characterized by FTIR spectroscopy and atomic force microscopy, respectively. The results suggested the possible presence of columnar structures when the electropolymerization is performed in the micellar medium.. (c) 2007 Wiley Periodicals, Inc.