In this study, Fe₂O₃ photoelectrode thin films were grown on fluorine-doped tin oxide substrates at various temperatures ranging from 145 to 220 °C using modified chemical bath deposition. The morphological, structural, electrical, and photoelectrochemical properties of the resulting Fe₂O₃ photoelectrode were analyzed using field emission scanning electron microscopy, X-ray diffraction, electrochemical impedance spectroscopy, and a three-electrode potentiostat/galvanostat, respectively. Growth temperature and hydrochloric acid etching both affected the growth of the Fe₂O₃ photoelectrode, with Fe₂O₃ thin film thickness first increasing and then decreasing as growth temperature increased. The pH value of the precursor solution varied according to growth temperature, which in turn affected film thickness. The highest photocurrent density (0.53 mA/cm² at 0.5 V vs. saturated calomel electrode) was obtained from the Fe₂O₃ photoelectrode grown at 190 °C, which yielded the thickest thin film, smallest full width at half maximum and largest grain size for the (104) and (110) plane, and highest flat-band potential value. Based on these findings, the photoelectrochemical properties of Fe₂O₃ photoelectrodes grown at various temperatures are strongly affected by their morphological, structural, and electrical properties.