PVDF was electrospun to fabricate ribbon-and spider web-like nanofibrous membranes containing both TiO2 nanoparticles and Ag nanoparticles. These composite fibrous membranes were characterised by scanning electron microscopy (SEM), confocal laser microscopy, transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The results revealed that Ag nanoparticles were mainly produced via reduction by DMF and played a key role in the formation of ribbon and spider web structures in cooperation with TiO2 nanoparticles. The presence of Ag nanoparticles was also found to improve the mechanical strength of the PVDF membranes. The photocatalytic degradation of methylene blue (MB) experimentals further shows that the Ag-TiO2/PVDF composite membranes have excellent photocatalytic activity which probably results from the synergistic effect of Ag and TiO2 nanoparticles. This typical composite membrane used as filters has potential applications in remove of organic pollutions in the industrial waster water areas.