It is challenging to explore a unified solution for the treatment of oily wastewater from complex sources. Thus, membrane materials with flexible separation schemes are highly desired. Herein, we fabricated a smart membrane by electrospinning TiO2 doped polyvinylidene fluoride (PVDF) nanofibers. The as-formed beads-on-string structure and hierarchical roughness of the nanofibers contribute to its superwetting/resisting property to liquids, which is desirable in oil/water separation. Switched simply by UV (or sunlight) irradiation and heating treatment, the smart membrane can realize reversible separation-of oil/water mixtures by selectively allowing water or oil to pass through alone. Most importantly, the as-prepared nanofiber membrane possesses outstanding antifouling and self-cleaning performance resulting from the photocatalytic property of TiO2, which has practical significance in saving solvents and recycling materials. This work provides a route for fabricating cost-effective, easily scaled up, and recyclable membranes for on-demand oil/water separation in versatile situations, which can be of great usage in the new green separation technology.