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Polaron formation, whereby an electron or hole strongly couples to a lattice distortion, inhibits the carrier mobility of many first-row transition metal oxide semiconductors. Recently reported XUV transient absorption measurements of hematite (α-Fe2O3) demonstrate formation of electron small polarons upon photoexcitation into an undistorted charge-transfer state followed by subpicosecond lattice reorganization. Here, we show that polaronic states of hematite can be accessed directly via optical transitions from the ground state in a th