Poly(vinyl alcohol) (PVA) and poly(tetrafluoroethylene) (PTFE) emulsion were blended with different mass concentrations and the blended spinning solutions were electrospun into composite nanofibers. The influence of the blend ratio of PVA to PTFE and electrospinning technical parameters on the morphology and diameter of the composite nanofibers were investigated. According to the result of thermogravimetric analyzer analysis, the composite membrane was sintered at 390 degrees C. The membranes were then characterized by differential scanning calorimetry, attenuated total reflection-Fourier transform infrared (ATR-FTIR), and scanning electron microscopy, respectively. The mechanical properties of the membranes before and after sintering were analyzed through tensile testing. The results show that the PTFE porous membranes could be electrospun effectively, thus demonstrating their potential application as filter media.