AbstractThe widely used stainless steels and their deformed variants are anticorrosive in ambient conditions due to passivation layers composed of chromium oxides. Conventionally, corrosion and erosion of the steels are attributed to the breakdown of such layers but seldomly to the origin that depends on surface heterogeneity at the microscopic level. In this work, the nanometer-scaled chemical heterogeneity at the surface unveiled via spectro-microscopy and chemometric analysis unexpectedly dominates the breakdown and corrosion behavior of the cold-rolled Ce-modified 2507 super-duplex stainless steels (SDSS) over its hot-deformed counterpart. Though relatively uniformly covered by a native Cr₂O₃ layer revealed by X-ray photoemission electron microscopy, the cold-rolled SDSS behaved poorly in passivity because of locally distributed Fe³⁺ rich nano-islands over the Fe/Cr oxide layer. This atomic-level knowledge provides a deep understanding of corrosion of stainless steel and is expected to benefit corrosion controls of similar high-alloyed metals.