Poly-(3,4-ethylenedioxythiophene) (PEDOT) films were electrodeposited by cyclic voltammetry and chrono amperometry on iron, mild steel and aluminium substrates, using a 0.1 M sodium dodecylsulfate (SDS) micellar aqueous solution as reaction medium. The passivating effect of sodium phthalate on iron and aluminium electrodes in SDS media was demonstrated also. Homogeneneous, regular, adhesive and thick (similar to 15 mu m) PEDOT films on Fe could be electrosynthesized in these conditions, The electropolymerization faradic yields ranged between 22 and 93% according to the current density value used. PEDOT films were characterized electrochemically and spectroscopically (XPS, IR and Raman spectra). Scanning electron microscopy (SEM) indicated that the films presented a cauliflower morphology. (C) 2000 Elsevier Science Ltd. All rights reserved.