The electrochemical behavior of nano and microcrystalline Fe-10Cr and Fe-20Cr alloys was determined using potentiodynamic polarization in 0.5 M H 2 SO 4 . Disks of the alloys were prepared by high-energy ball milling followed by compaction and sintering. In the current study, nanocrystalline Fe-Cr alloys reveal significantly different electrochemical characteristics, typified by lower anodic current densities and more negative passivation potentials, compared with their microcrystalline counterparts. In addition to the differences in grain boundary density, compositional characterization of corrosion films carried out by X-ray photoelectron spectroscopy indicates a higher Cr content in the film developed upon nanocrystalline Fe-Cr alloys. Mechanisms for observed enhancement in the corrosion performance of the nanocrystalline Fe-Cr alloys are discussed.