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Ultraviolet photolysis (UVC, 254 nm) was coupled with an electrochemical oxidation process to degrade three kinds of veterinary sulfonamide (sulfamethazine [SMZ] tablets, sulfamonomethoxine [SMM] tablets, and compound sulfamethoxazole [SMX] tablets). The treatment was applied using a flat ceramic microfiltration membrane to study the effects of photocatalysts. The effectiveness of degradation of the three sulfonamides was evaluated under different conditions. Dissolved oxygen was provided via aeration, but this resulted in a large decrease in the degradation effectiveness due to the inhibition of free chlorine electrogeneration. The photocatalysts had no promotional effect on sulfonamide removal from wastewater due to reduced UV penetration. Because of the different distribution coefficients of sulfonamides, UV irradiation had different effects on different sulfonamide species. For SMZ and SMM, anionic species exhibited a higher degradation rate, whereas for SMX, degradation was most effective for neutral species. In addition, the free chlorine yield increased as the pH increased. Free chlorine conversion reactions occurred under UV irradiation, with the reactions possibly restrained by sulfonamides. Reactive chlorine species promoted SMM degradation. Compared to UV irradiation or electrochemical oxidation alone, the UV/in-situ electrochemical oxidation process was more effective and is suitable for treating real wastewater under various environmental pH levels.