We proposed a facile and robust strategy for fabricating tubular polytetrafluoroethylene (PTFE) / poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) ultrafine fibers-covered porous membranes for continuous oil/water separation via electrospinning-sintering method. Specifically, PTFE/FEP/poly (vinyl alcohol) (PVA) ultrafine fibers were electrospun covering on a porous supporting tube which served as the outer layer of the porous membranes. Manipulation of shapes by control of FEP additions enabled the creation of PTFE porous membranes with optimized membrane pore structure during the sintering process. Meanwhile, the obtained membranes had excellent oil/water selectivity in oil/water separation. Moreover, they could effectively separate surfactant-stabilized water-in-oil emulsions with separation efficiency as high as 99.9% and high flux (134 L m(-2).h(-1) at 0.5 bar). Therefore, tubular PTFE/FEP ultrafine fibers-covered porous membranes enabled an efficient separation for various oil/water emulsions, showing attractive potential for practical oil/water separation.