Cobalt hexacyanoferrate (CoHCF) nanostructure was synthesized by anodic oxidation of metallic cobalt nanoflowers in a solution of K3Fe(CN)(6). The synthesized CoHCF sample was then employed to prepare a modified carbon paste electrode. The modified electrode was characterized electrochemically in a phosphate buffer solution at physiological pH. Two redox transitions were appeared in the voltammograms which were related to the redox processes of Co-II/Co-III and Fe-II/Fe-III in the solid state of CoHCF. The modified electrode was successfully applied to the electrooxidation of nitrite and sulfite and these substrates were oxidized electrocatalytically on the modified electrode surface via the active Fe-III species. The catalytic rate constants, the electron transfer coefficients and diffusion coefficients involved in the electrocatalytic oxidation of the compounds were reported. The modified electrode was applied to the amperometric determination of nitrite and sulfite. (C) 2012 Elsevier Ltd. All rights reserved.