Photoelectrochemical (PEC) degradation of Procion Red MX-5B was investigated in aqueous Na2SO4 solution. Higher electrolyte concentration resulted in higher current between the electrodes due to increased conductivities of the solutions. UV irradiation could obviously raise the current, and the differences became larger in accordance with the increase of the applied potentials. The pH declined in the first 30 minutes and became constant for the prolonged reaction time during both PEC degradation and photocatalytic oxidation. The applied potential could only slightly improve dye decolorization. Although a potential of 8 V was applied to 0.3 mol/l Na2SO4 solution, TOC removal efficiency of PEC degradation was almost as the same as that of photocatalytic oxidation.