The electrochemical deposition of mixed Ni-x-Fe(1-x)Fe(CN)(6) thin films on a glassy carbon (GC) electrode surface were carried out by electro-deposition under continuous potential cycling condition for the first time. The redox potential of the low spin iron in the hybrid film was found to depend on the ratio of metal centres. The improvement in the electrocatalytic property of the nickel hexacyanoferrate film with incorporation of iron ions in the film towards the electrocatalysis of hydrogen peroxide was studied in electrolytes like KNO3 and NaNO3. The stability of hybrid film in Na+ containing supporting electrolytes was examined. Detection limit of H2O2 was about 1 mu M as determined by amperometry with the sensitivity of 192 nA/mu M. The chemically modified glassy carbon electrodes with NixFe(1-x)HCF hybrid films were characterized by cyclic voltammetry, impedance spectroscopy, energy dispersive X-ray analysis etc. These films may find extensive applications as redox mediators in biosensors which employ oxidase enzymes. (C) 2011 Elsevier B.V. All rights reserved.