With improved hydrophilicity poly(vinylidene fluoride) (PVDF)-based membranes acted as ultrafiltration membranes, it was of great benefit to reduce the fouling degree and prolong the service life. In this study, the hydrophilic polyethylene oxide (PEO) and titanium dioxide (TiO2) nanoparticles were incorporated into the PVDF polymer matrix. The PEO/PVDF and TiO2/PEO/PVDF fibrous membranes were fabricated via an electrospinning process. The characterizations including scanning electron microscopy (SEM), contact angle measurements, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and thermal gravimetric analysis (TGA) were used to assess the impact of the performance and characteristics of the modified PVDF ultrafiltration membrane. We optimized the performance of blending modification and believed that this new method could be promising for preparing the ultrafiltration membrane. Further, the effects of the addition of TiO2 nanoparticles or PEO into the PVDF casting solution on the properties, such as pure water flux and photocatalytic degradation properties were investigated in detail. The results showed that the TiO2/PEO/PVDF composite ultrafiltration membranes have better water flux and photocatalytic degradation properties under low pressure.