Polyelectrolyte multilayer films composed of a polycation (poly(allylamine hydrochloride) PAH) and a polyanion (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) PEDOT:PSS) were prepared by a spin self-assembly method, and their electrochemical and electrochromic properties were investigated. The change in the surface charge and the optical absorption spectra of the multilayer films revealed that sequential deposition of polyelectrolyte was successfully achieved during the spin self-assembly. The electrochromic properties of 20-bilayered PAH/PEDOT:PSS were also investigated. The response time for the coloring and bleaching processes was 6.2 and 2.5 s, respectively, and the coloration efficiency was 199.3 cm(2)/C. These results indicate that a spin self-assembly process could be a viable alternative for the fabrication of electrochromic devices. (C) 2008 Elsevier B.V. All rights reserved.