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Membrane separation has been widely utilized to eliminate pollutants from wastewater. Among them, a polyacrylonitrile (PAN) ultrafiltration (UF) membrane has presented outstanding stability, and distinguished chemical and thermal properties. However, UF membranes inevitably incur fouling issues during their operation procedure caused by contaminant adhesion on the membrane surface, which would restrict the operational efficiency and increase the maintenance cost. The conventional physical and chemical cleaning is not an effective technique to reduce the fouling due to the additional chemical addition and inevitable structure damage. Recently, UF membranes combined with photocatalytic materials are suggested to be a useful approach to conquer the membrane fouling issues. Herein, TiO₂ nanoparticles were utilized to blend with a PAN casting solution for fabricating a composite UF membrane via a phase inversion method. With a certain TiO₂ addition, the obtained membranes presented an enhancement of hydrophilicity, which could promote the water permeability and antifouling performance. The optimized M3 membrane prepared with 15.0 wt% PAN and 0.6 wt% TiO₂ exhibited an excellent water permeability up to 207.0 L m⁻² h⁻¹ bar⁻¹ with an outstanding 99.0% BSA rejection and superior antifouling property. In addition, the photocatalytic TiO₂ nanoparticles endowed the M3 membrane with a remarkable self-cleaning ability under the UV irradiation. This facile construction method offered new insight to enhance the UF membrane separation performance with an enhanced antifouling ability.