MXene, a recently emerged 2D material, has garnered substantial attention for a myriad of applications. Despite the growing interest, there remains a noticeable gap in exploring MXene-based membranes for the simultaneous achievement of photomodulated oil/water separation, bacterial resistance, and the removal of pollutants in the treatment of oily wastewater. In this work, we have successfully synthesized a novel multifunctional CuO@MXene-PAN nanofibrous membrane (NFM) featuring unique nanograin-like structures. Benefitting from these unique structures, the resultant membrane shows excellent superwetting properties, significantly enhancing its performance in oil/water separation. In addition, the membrane's photothermal property boosts its permeance by 40% under visible light illumination within 30 min. Furthermore, the resultant membrane shows decent dye removal efficiency in an aqueous solution, e.g., Rhodamine B (RhB), promoting efficient degradation with high reusability under visible light. Most remarkably, the resultant membrane exhibits superior antibiofouling capability and consistently resists the adhesion of microorganisms such as cyanobacteria over a 14 day period. Thus, the combined effect of superior superwetting properties, photothermal responsivity, photocatalytic activity, and the antibacterial effect in CuO@MXene-PAN NFM contributes to the efficient treatment of intricate oily wastewater. This synergistic combination of superior properties in the membrane could be an appealing strategy for the broad development of multifunctional materials to prevent fouling during actual separation performance.