In this paper we investigate the electrochemical behavior of iron hexacyanocobaltate (FeHCC) in comparison to the cobalt hexacyanoferrate (CoHCF). The best results were achieved on electrochemical synthesized film of FeHCC on the TiO2 modified electrodes. The chemical and physical characterizations confirm the formation of the FeHCC with the classical cubic crystal structure of the Prussian blue analogs, with cell parameter a very close to 10 A, as well as the formation of micro aggregates of TiO2 covered by FeHCC. The synthesis was performed on various substrates such as glassy carbon (GC), graphite foil (GF) and indium tin oxide (ITO) in order to develop new technological applications. (C) 2014 Elsevier B.V. All rights reserved.