The electrocatalytic reduction of Fe(III) was investigated using a carbon fibre microelectrode modified with a ruthenium oxide hexacyanoferrate film (RuOHCF/CFM). At surfaces containing this chemical modifier, Fe(III) is electrocatalytically reduced at 0.0 V without interference from Fe(II), hence allowing the speciation of Fe(III). A linear relationship between the cathodic current and concentration of Fe(III) was obtained by amperometry in the range 10-210 mu mol L-1 with detection and quantification limits of 0.22 (S/N= 3) and 0.74 (S/N= 10) mu mol L-1, respectively. The described amperometric method was successfully applied for the determination of Fe(III) in different wine samples. (C) 2014 Elsevier B.V. All rights reserved.