Polytetrafluoroethylene (PTFE) fibers are widely used in the textile industry, filter media, membrane distillation, electronic appliances, and construction. In this study, PTFE-polyethylene oxide (PEO) fibrous membranes were fabricated by emulsion electrospinning; subsequently, pure PTFE nanofibers were obtained via sintering. PTFE-PEO electrospinning solutions were prepared using different weight ratios to determine the optimized condition. As the ratio of the PEO increased, the fiber structure improved. Scanning electron microscopy and Fourier-transform infrared spectroscopy observations indicate that PEO is removed and PTFE fused gradually to form bonds among them during sintering. The obtained pristine PTFE membrane demonstrated hydrophobicity at 143.6° water contact angle and oleophilicity at 0° oil contact angle, which is known to be utilized for oil/water separation. A simple separation experiment was performed to remove oil droplets from water. The PTFE membrane exhibited good chemical stability and a high surface-area-to-volume nanofiber ratio. These excellent properties suggest that it is applicable to oil/water separation in harsh chemical environments.