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The oxide layers on stainless steel formed by heating at various high temperatures and by dipping in LiF+BeF2 molten (Flibe) bath at 600°C were characterized by CEMS. Hematite was a major iron product at 600°C and fine oxides with paramagnetic Fe(III) species were produced at the higher temperatures than 700°C. The interface of stainless steel beneath oxide films was characterized as the hyperfine field distributions. Paramagnetic Fe(III) species were produced on Cr depleted layers in the Flibe bath. CEMS is effective for simultaneous characterization of both oxide surface and interface layers of the ferritic stainless steel.