This study uses PVDF, PAN, and coaxial electrospinning technique to build a core-sheath structure for TiO2@PVDF/PAN electrospun membranes. The resulting electrospun membranes are compared with traditional electrospun membranes in terms of photocatalysis and oil-water separation, which examines the influences of electrospinning fibrous structure. The test results show that the core-sheath structure provides TiO2@PVDF/PAN electrospun membranes with a large diameter, high strength, a rough surface, a high photocatalysis, and good oil-water separation. With PVDF as the sheath and PAN as the core, TiO2@PVDF/PAN electrospun membranes have a maximum strength of 8.96 MPa and exhibit 97% of rhodamine B pollutant after the exposure to the UV light. Moreover, the oil-water separation rate is 99% and an oil flux is 40 163.79 L center dot m(2)center dot h(-1), and the membrane maintains a high flux after 10 cycles, which makes TiO2@PVDF/PAN electrospun membranes an important candidate for treating wastewater produced in industry and daily life.