As a kind of high-performance fibers, PTFE fiber has been widely used in many fields because of its unique characteristics. In this study, the poly(tetrafloroethylene) (PTFE) nanofibers manufactured by electrospinning method was reported. The gel-spinning solution of poly(tetrafluoroethylene)/poly(vinyl alcohol)/boric acid (PTFE/PVA/BA), which was prepared by the gel process of the mixture of PTFE, PVA, BA and redistilled water, was electrospun to form PTFE/PVA/BA composite nanofibers. After calcinating, the PTFE nanofibers with diameters of 200 nm to 1000 nm were obtained. The fibers before and after calcinating were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), FT-IR spectrum analysis and X-ray photoelectron spectroscopy (XPS), respectively, and the mechanical and hydrophobic properties of the fibers were also investigated. The results showed that the PTFE nanofiber membranes could be electrospun effectively used the gel-spinning solution of PTFE/PVA/BA, and may realize the applications in the fields of high-temperature filtration, catalyst supports, battery separator and so on.