Electrodeposited nanocrystalline and conventional polycrystalline NiFe alloys of similar iron content were investigated to understand the effect of grain size on the corrosion behaviour of these materials. Potentiodynamic polarization testing in 1 N H2SO4 revealed similar active-passive-transpassive behaviour with negligible differences in the Tafel and transpassive regions regardless of grain size. It is shown that differences in the region of active dissolution are the result of strong contributions of sulfur impurities in the nanocrystalline electrodeposits rather than being due to grain size alone.