In this study, electrospun polyvinylidene fluoride (PVDF)-based nanofibrous membranes embedding TiO2 wereprepared and used for photocatalytic degradation and oil/water separation. The nanofibrous membranes were characterizedby scanning electron microscopy (SEM), transmission electronic microscope (TEM), X-ray diffraction (XRD), Fouriertransform infrared spectroscopy (FTIR) spectroscopy, thermal performance analysis, and oil/water separation analysis. Andthe degradation of rhodamine B dye was also investigated. Results showed that the fiber diameter and thermal stability of themembranes decreased with the increasing of TiO2. Meanwhile, the fiber surface roughness and specific surface areaincreased. The analysis of TEM, XRD and FTIR indicated that TiO2 existed in the PVDF membranes. When the TiO2 contentwas 12 %, the fiber diameter of the membranes was about 110 nm, and the photocatalytic degradation of rhodamine B dyeefficiency was up to 97 %. The reaction rate constant was 0.02057 min-1. At 0.01 MPa vacuum, oil separated from watereffectively, which proves that separation can be easily conducted with a low energy cost. Thus, the prepared membranes havea very high application prospect in the purification of reclaimed water and separation of oil and water.