To optimize the uniform dispersion of nanoparticles and enhance their catalytic degradation effect on small molecule dyes in textile wastewater, titanium dioxide (TiO2) was deposited on polyacrylonitrile (PAN) fiber membranes using magnetron sputtering technology, and TiO2/PAN nanofiber membrane (NFM) with low content and high catalytic efficiency was successfully prepared. Through membrane separation coupling electrocatalysis, the composite membranes exhibited outstanding performance in removing Congo red (CR), Sunset yellow (SY), Methyl orange (MO), and Methylene blue (MB) dyes, with removal rates of 99.5%, 98.8%, 98.5%, and 87.2% respectively. Even after continuous catalysis for 10 h, the composite membranes maintained a high dye removal rate, demonstrating their remarkable stability and water treatment capabilities. Furthermore, TiO2/PAN NFMs displayed high pure water permeance, dye permeance, and mechanical strength. Specifically, M20 (magnetron sputtering time of 20 min) showed water permeance and dye (SY) permeance values of 1944 L·m-2·h-1·bar-1 and 816 L·m-2·h-1·bar-1, respectively, and indicate superior mechanical and electrochemical properties. During the electrocatalytic process, TiO2/PAN NFMs generated reactive oxygen species (ROS) on the surface, imparting a self-cleaning property that extended the service life of the membranes and offered an effective solution for textile wastewater treatment.