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-DTG-DTA，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.