Purification of dye wastewater by combining photocatalytic degradation with solar energy-driven interfacial water evaporation has emerged as a promising approach to address water pollution in recent years. In this work, a high-performance polymer, polyarylene ether nitrile (PEN), was electrostatically spun to construct a robust nanofibrous substrate, then dual-functionalized using polyaniline (PANI) and titanium dioxide (TiO2) via a facile polydopamine (PDA)-assisted vacuum self-assembly method. Moreover, the CA of the PEN membrane after PDA and PANI@TiO2 treatment changes from 20° to 0° within 0.4s, showing superhydrophilic properties and providing rapid water supply for water evaporation. PANI and TiO2 were employed as the photo-thermal conversion component and photocatalytic component, respectively. The fabricated dual-functionalized PANI@TiO2/PEN composite nanofibrous membrane exhibited a high water evaporation rate of up to 3.23kgm-2 h-1 under a simulated solar illumination of 1 KW m-2. Owing to the reduction in the photoelectron-hole recombination rate promoted by PANI, the composite nanofibrous membrane demonstrated a favorable dye removal rate of 92.18% in 6h for methylene blue (MB). Furthermore, the robust PEN nanofibrous skeleton conferred the composite membrane with thermal resistance and corrosion resistance properties, ensuring long-term performance in harsh environments. The facile fabricated PANI@TiO2/PEN membrane achieved comprehensive performance, offering a promising strategy by combining solar-driven interfacial water evaporation and photocatalytic degradation for water purification.