The organic-inorganic material consisted of poly(3,4-ethylenedioxythiophene) (pEDOT) and copper hexacyanoferrate (Cuhcf) was synthesized. The pEDOT film with Fe(CN)(6)(3-/4-) as counter-ions potentio-dynamically polarized in aqueous CuCl2 electrolyte brings about stable hybrid material (pEDOT/Cuhcf) performing single redox activity of Fe-II/III at a formal potential E-f = 0.61 V (vs. Ag/AgCl/0.1 M KCl) and less clearly shaped two redox coming from copper ions entrapped inside the film. XPS ex situ measurements show three different binding energies for copper (Cu 2p(3/2): 932.2, 934.8 and 936.3 eV) and two for iron (Fe 2p(3/2): 708.2 and 709.0 eV). Spectroelectrochemical measurements allowed to establish an order in the energy band gap (E-g) for the investigated hybrids pEDOT/Mehcf (Me = Fe, Co, Ni, Cu) as follows: E-g(pEDOT/Fehcf) = 1.40 eV < E-g(pEDOT/Cohcf) = 1.48 eV < E-g(pEDOT/Nihcf) = 1.52 eV < E-g(pEPOT/Cuhcf) = 1.6 eV. The hybrid materials were examined as electrodes for electrocatalytic reduction of H2O2. Copper centres in pEDOT/Cuhcf as well as high spin iron centres in pEDOT/Fehcf were found to be electrocatalytically active towards hydrogen peroxide reduction. (C) 2011 Elsevier Ltd. All rights reserved.