Poly (3,4-ethyl enedioxythiophene) (PEDOT) films have been electropolymerized from an aqueous micellar solution comprising camphorsulfonic acid (CSA), lithium trifluoromethanesulfonate (LiCF3SO3) and EDOT. The inclusion of the dopants CS- and CF3SO3- in the polymer structure and an unusually high doping level of 0.54 have been ascertained by the X-ray photoelectron spectroscopy. Transmission electron microscopy and atomic force microscopy studies show that the micellar effect of CSA leads to a morphology wherein polymer particles link together to form elongated shapes and also endows the film with a surface roughness of 25-30 nm. These nanostructures permit a facile intercalation-deintercalation of anions in the film during redox cycling. Electrochemical impedance spectroscopy show that the charge transfer phenomenon at the PEDOT-electrolyte interface is dominant in the high frequency region and diffusion controlled ionic movement prevails in the low frequency regime. The use of these films as potential cathodes in electrochromic windows is rationalized not only on the basis of their high scalability and ease of processing but also due to their large coloration efficiency (123 cm(2) C-1) and transmission modulation (50%) at a photopic wavelength of 550 nm. But further improvement in color-bleach kinetics and reproducibility of redox behavior is desirable to broaden their spectrum of utility. (C) 2007 Elsevier Ltd. All rights reserved.