Passive films formed on single grains of a polycrystalline pure iron substrate were investigated in 0.05 mol dm(-3) sulfuric acid with a micro-capillary cell (MCC). Passivation behavior under the condition of potentiostatic polarization was strongly dependent on the crystallographic orientation of the substrate surface. Electrochemical impedance spectroscopy revealed that the charge transfer resistance of the passivated surface was determined by the substrate orientation. Galvanostatic reduction and XPS analysis of the surface passivated using the MCC showed that the substrate orientation affected the chemical state of iron in the oxide. The results suggested that the aging of the passive film formed on the iron substrate depended on its crystallographic orientation due to the differences in surface energy of the substrate surface that has a bcc lattice structure. It was concluded that the grain dependency on the electric property of the passive film arose from the compositional differences of the oxide film. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.