The effect of EDTA (ethylenediaminetetraacetic acid, added as Na(2)EDTA) on the electrochemical behavior of iron and on the semiconducting properties of passive films formed on this metal in berate buffer solution (pH 8.4) was studied. Electrochemical studies, including potentiodynamic and galvanostatic reduction experiments and capacitance measurements coupled with Mott-Schottky analysis, were carried out over the entire passive range in berate buffer solutions in the presence and absence of 0.01 M EDTA. Passive films formed in the presence of EDTA were thinner and showed higher donor concentrations. EDTA present in the berate buffer solution effectively inhibited the formation of the Fe(III) outer layer, thereby rendering the defective Fe3O4 inner layer to direct examination. The barrier layer is found to be an n-type semiconductor, which is consistent with the oxide being a defective magnetite in which the principal defects are oxygen vacancies and cation interstitials. EDTA effectively competes with chloride ion for adsorption into oxygen vacancies at the barrier layer/solution interface, thereby suggesting that the chelating agent might be an effective inhibitor of passivity breakdown.