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Magnetite and hematite iron oxides are minerals of great economic and scientific importance. The oxidation of magnetite to hematite is characterized as a topotaxial reaction in which the crystallographic orientations of the hematite crystals are determined by the orientation of the magnetite crystals. Thus, the transformation between these minerals is described by specific orientation relationships, called topotaxial relationships. This study presents electron-backscatter diffraction analyses conducted on natural octahedral crystals of magnetite partially transformed into hematite. Inverse pole figure maps and pole figures were used to establish the topotaxial relationships between these phases. Transformation matrices were also applied to Euler angles to assess the diffraction patterns obtained and confirm the identified relationships. A new orientation condition resulting from the magnetite–hematite transformation was characterized, defined by the parallelism between the octahedral planes {111} of magnetite and rhombohedral planes of hematite. Moreover, there was a coincidence between one of the octahedral planes of magnetite and the basal {0001} plane of hematite, and between dodecahedral planes {110} of magnetite and prismatic planes of hematite. All these three orientation conditions are necessary and define a growth model for hematite crystals from a magnetite crystal. A new topotaxial relationship is also proposed: (111)Mag || (0001)Hem and || .