Electrochemical method to obtain poly(3,4-ethylenedioxythiophene) modified by poly(styrenesulfonate) and silver hexacyanocobaltate (pEDOT/PSS: AgCoCN) in one step-procedure is shown. The electroactive film was obtain from the Ag-3[Co(CN)(6)] suspension containing monomer and anionic surfactant. The electrode material was characterized by SEM, EDX and AFM techniques while the electrochemical performance of pEDOT/PSS: AgCoCN film was tested by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. (C) 2012 Elsevier B.V. All rights reserved.