Poly(3,4-ethylenedioxythiophene) (PEDOTh) films were potentiodynamically deposited on platinum from tetrabutylammonium hexafluorophosphate/acetonitrile Solutions. Polymers prepared with different number of cycles showed reversible redox behaviour and the X-ray Photoelectron Spectroscopy (XPS) characterization revealed the existence of zones with different conductivity and confirmed the presence of PF6-. The incorporation of the metallic complex Fe(CN)(6)(3-) in the PEDOTh films was made in one step, after the electrosynthesis of a film grown with a given number of potential cycles, and by means of polymerization/incorporation sequences. XPS data confirmed the presence of the inorganic species and the highest Fe 2p(3/2) peak intensity was observed for thin films (30 cycles) when the one step incorporation has been used. The XPS results suggest a partial dissociation of the Fe-(C-N) bond of the complex in the modified electrodes. (C) 2009 Elsevier B.V. All rights reserved.