A series of flexible polyacrylonitrile/TiO2 (PAN/P25) multi-porous nanotubular membranes were successfully constructed by facile electrospinning combined with an ethylene glycol solvothermal induce strategy. The effects of P25 dosage and solvothermal time on the morphology of samples were systematically investigated, which were characterized in terms of surface morphology, microstructure, specific surface area, thermal analysis, wettability, photoelectrochemical and fluorescence spectra. Rhodamine B (RhB) and Escherichia coli (E. coli) were employed as simulated pollutants to evaluate photocatalytic degradation and antibacterial properties of the PAN/P25-3 multi-porous nanotubular membrane. The PAN/P25-3 membrane exhibited the highest photocatalytic degradation efficiency, with 96.1% degradation of RhB within 120 min under a xenon lamp light source and a photocatalytic inactivation rate of 95.8% for E. coli under 365 nm monochromatic light irradiation. The photocatalytic degradation mechanism of the PAN/P25-3 multi-porous nanotubular membrane for RhB was deduced from the results of 3D-EEM fluorescence and scavenger experiments of reactive species. Additionally, the cyclic photodegradation experiments demonstrated that the PAN/P25-3 membrane maintained excellent stability and photocatalytic performance after multiple degradation cycles, confirming its potential for sustainable wastewater treatment applications.