Abstract: The TiO₂(P25) semiconductor mineral electrode was used to study the photocatalytic reduction of U(Ⅵ) with low-molecular-weight organics (formic acid, methanol, acetic acid, ethanol) and formic acid at different concentrations (0, 20, 40, 60, 80, 100 mmol/L) as hole scavengers, respectively. The results indicate that due to the higher ionizing ability, the hole scavenging capacity of low-molecular-weight organic acid is stronger than that of low-molecular-weight alcohol. In addition, all hole scavengers studied in this paper can improve the reduction rate of U(Ⅵ) and formic acid is best with the reduction rate as high as 90.26% at 60 mmol/L. SEM and EDS results show that some squares of uranium minerals were formed after photocatalytic reaction, which were adsorbed on the electrode surface and occupied active sites of TiO₂. Electrochemical impedance spectroscopy (EIS) analysis indicates that mineral semiconductor electrode exhibits a higher electron transport resistance ability after photocatalytic reaction.