Novel poly(tetrafluoroethylene) (PTFE) hollow fiber membranes were successfully fabricated by electrospinning, with ultrafine fibrous PTFE membranes as separation layers, while a porous glassfiber braided tube served as the supporting matrix. During this process, PTFE/poly(vinylalcohol) (PVA) ultrafine fibrous membranes were electrospun while covering the

porous glassfiber braided tube; then, the nascent PTFE/PVA hollow fiber membrane was obtained. In the following sintering process, the spinning carrier PVA decomposed; meanwhile, the ultrafine fibrous PTFE membrane shrank inward so as to further integrate with the supporting matrix. Therefore, the ultrafine fibrous PTFE membranes had excellent interface bonding strength with the supporting matrix. Moreover, the obtained ultrafine fibrous PTFE hollow fiber membrane exhibited superior performances in terms of strong hydrophobicity (CA > 140), high porosity (>70%), and sharp pore size distribution. The comprehensive properties indicated that the ultrafine fibrous PTFE hollow fiber membranes could have potentially useful applications in membrane contactors (MC), especially membrane distillation (MD) in harsh water environments.