Abstract: Hematite (α−Fe₂O₃) photoanode has been obtained through hydrothermal method. The physical and photophysical properties of the hematite photoanode were investigated by X−ray diffraction (XRD), UV−vis absorption spectroscopy, scanning electron microscopy (SEM) and the photo−electrochemical performance has been also evaluated. In terms of maximizing the photoelectrochemical performances of the hematite photoanodes, the preparation conditions were optimized. The photoelctrochemical performances of hematite photoanode can be improved by the electrochemical surface pretreatment, and a possible mechanism has been proposed to explain the reason for the improvement of photoelctrochemical performances, which is attributed to the favorable photohole transfer and the reduced electron−hole recombination.