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In this work, a simple one-step hydrothermal method was employed to prepare the Ce-doped Fe₂O₃ ordered nanorod arrays (CFT). The Ce doping successfully narrowed the band gap of Fe₂O₃, which improved the visible light absorption performance. In addition, with the help of Ce doping, the recombination of electron/hole pairs was significantly inhibited. The external voltage will make the performance of the Ce-doped sample better. Therefore, the Ce-doped Fe₂O₃ has reached superior photoelectrochemical (PEC) performance with a high photocurrent density of 1.47 mA/cm² at 1.6 V vs. RHE (Reversible Hydrogen Electrode), which is 7.3 times higher than that of pristine Fe₂O₃ nanorod arrays (FT). The Hydrogen (H₂) production from PEC water splitting of Fe₂O₃ was highly improved by Ce doping to achieve an evolution rate of 21 μmol/cm²/h.