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Oxidation of a Fe –13Cr alloy under water vapor at 600°C produced a zone of nano-sized precipitation underneath the outside scale formed by iron oxides and Fe–Cr spinel. The majority of the spinel layer shows a fixed orientation relationship to the ferritic matrix: {1 0 0}α || {1 0 0}sp & <0 1 1>α || <0 0 1>sp . However, also the discovered precipitated particles are characterized by the same crystallographic orientation relationship to the respective ferritic parent grain. The habit of the precipitates is best described by a lath morphology with their main axis parallel to <1 0 0> of ferrite. Energy dispersive X-ray spectroscopy (EDX) and electron backscatter diffraction (EBSD) in scanning electron microscope (SEM) have been applied to characterize the oxide layer in micrometer scale. The clearly smaller precipitates were subsequently investigated by transmission electron microscopy (TEM). Specimens have been prepared by focused ion-beam (FIB) milling at an area previously characterized by EBSD. They cover the ferritic base material, but mainly the precipitation zone and the Fe–Cr spinel layer. Energy filtered selected area diffraction (SAD) in the conventional (C)TEM and high-angle annular dark field (HAADF) imaging in the scanning (S)TEM mode were employed in the characterization of the specimens.