The dissolution behavior of the Fe-Cr alloys in acidic Na2SO4 solutions was investigated using online inductively coupled plasma-optical emission spectrometry (ICP-OES). The dissolution current density of pure Fe measured by spectroscopic analysis shows an anodic Tafel slope of 60 mV decade–1, while the anodic Tafel slope of Fe species in Fe-Cr alloys increases to 120 mV decade–1 with increasing Cr content in the alloy, suggesting that the rate-determining step of the anodic reaction mechanism is dependent on the Cr content. The mass balance on the surface of Fe-6Cr in the active-passive transition indicated that Cr species preferentially dissolved through a salt layer formed on the alloy surface. Some oxidized products that existed in the salt layer in the active region dissolved when the surface changed to the passive state. The anodic reaction mechanism and passivation processes of Fe-Cr alloys, including pure Fe, are discussed quantitatively.