The electropolymerized polypyrrole films formed from micellar solution of anionic surfactants, viz., Dodecylbenzene sulfonate(DBS), showed potential-dependent anion and cation ion switching behavior and the peculiar columnar structure. The formation process and the redox of the polypyrrole was studied with the in situ atomic force microscopy (AFM) and electrochemical quartz crystal microbalance(EQCM) methods. In-situ AFM observation clearly indicated that such a columnar structure started to form around critical charge densities of 60-100 mC cm−2. The cyclic voltammogram for the PPy doped with DBS− film showed two redox couples, each of which corresponds to a cation and an anion exchange process. Thus, the film behaves as a dual-mode ion doping/undoping exchanger. As the PPy film was prepared in higher concentration of the surfactant dopant, where the micelles are formed in solution, the resulting film showed a considerably higher(ca. three orders of magnitude) diffusion coefficient compared to ordinary PPy films so far reported. Such an enhanced diffusivity of ions could be attributed to a peculiar structure of the polymer formed. The feasibility of such polypyrrole in use of supercapacitor material was discussed.