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We studied magnetite–hematite–magnetite transformations in an ultrathin epitaxial film on Pt(111) using surface sensitive and bulk sensitive methods. At initial oxidation stages at elevated temperature (810 K), a 5-nm thick magnetite Fe3O4(111) film became non-stoichiometric toward maghemite and then showed the first signs of hematite phase formation under an oxygen exposure of 3 × 103 L. Finally, under 2 × 104 L, the film fully transformed to hematite α-Fe2O3(0001), maintaining a high single-crystal quality. A comparison of the conversion electron Mössbauer spectra and low energy electron diffraction pattern showed that at intermediate oxidation stages, hematite dominated at the surface, whereas a spinel phase was still observed in the deeper layers. The magnetite–hematite conversion was fully reversed by annealing under ultra-high vacuum at temperatures exceeding 600 K, and despite a change in morphology, the magnetite film preserved the original crystal structure and orientation. [ABSTRACT FROM AUTHOR]