Polyvinyl alcohol (PVA)/ polytetrafluoroethylene (PTFE)/SiO₂ oil- water separation fiber membranes with superhydrophobic properties were prepared by electrostatic spinning. The PVA/PTFE fiber membranes were constructed by using SiO₂ particles as secondary rough structure, and PVA/PTFE/SiO₂ composite fiber membranes were obtained. The composite fiber films were characterized by XRD，hydrophobic angle test，SEM，EDS，TG-DTGDTA，FT-IR and XPS. The oil-water separation and chemical stability were tested. The results show that the addition of SiO₂ particles improves the hydrophobic performance of the fiber membranes. When the mass ratio of SiO2 particles is 0.5%, the average hydrophobic angle of the fiber membrane reaches the maximum of 158.9°. The separation efficiency of the composite membrane for different oil-water mixtures is above 99.2%, and the efficiency remains above 98.6% after 20 cycles of separation. It shows great application potential in oil- water separation, and also has excellent chemical stability properties.