In this paper, titanium dioxide (TiO2)/quaternary phosphonium salts (QPS)/polyacrylonitrile (PAN) composite nanofibrous membranes were prepared through electrospinning to fabricate organic and inorganic complex highly efficient antibacterial and ultraviolet (UV)-resistant membranes. The composite material derived from QPS was designed effectively kill bacteria and improve quaternary ammonium salts' drug-resistant problem, while the addition of TiO2 can absorb ultraviolet light to catalyze sterilization and decompose residues. The obtained membranes were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transfer infrared spectroscopy (FTIR), thermogravimetric analysis (TG), ultraviolet protection factor (UPF), and antibacterial tests. SEM images indicate slim and uniform morphology of fibers with a diameter of 0.1-0.2um. FTIR and XPS tests confirm the existence of QPS and TiO2 compounds in the composite membranes, and there is no chemical bond between these substrates and PAN. TG test implies that the membranes have a good thermal stability. UPF of 1648.1 and UVA transmittance of 0.28% indicate that the TiO2/QPS/PAN membranes have an extraordinary UV resistance property. The antibacterial tests show that complex membranes have 99.99% antibacterial rate against both gram-negative Escherichia coli and gram-positive Staphylococcus aureus.