Membrane separation technology is used to treat environmental wastewater, but during the treatment process, the occurrence of membrane fouling greatly affects the treatment efficiency. To address this phenomenon, improve membrane antipollution capabilities, and treat organic wastewater, photocatalysis and membrane separation technology have been coupled, forming a suitable and promising treatment method. Here, we propose a simple strategy to prepare a polyvinylidene fluoride/polyvinyl pyrrolidone nitrogen-doped titanium dioxide fibrous membrane (PVDF/PVP N-doped TiO2 fibrous membrane). The experimental results showed that PVDF and PVP mixed spinning made the fibrous membrane have a unique microstructure, and the superhydrophobic PVDF fibrous membrane was changed into superhydrophilic. In addition, electrospraying technology was used to attach TiO2 nanoparticles (NPs) to the fiber, and nitrogen (N) was doped in this process to improve the photocatalytic activity of the fibrous membrane. Finally, methyl blue solution was used as the target organic pollutant. Under the irradiation of a xenon lamp, 90.05% of methyl blue was removed within 90 min, indicating that the membrane had good photocatalytic performance. In a water contact angle test, the PVDF/PVP N-doped TiO2 fibrous membrane showed superhydrophilicity. The design of a fibrous membrane with high photocatalytic activity and superhydrophilicity properties has great potential for practical application in the purification of industrial wastewater.