Ideal membranes toward separation of stable oil/water emulsions should have surface hydrophilicity and submicron pores in the separating layer. However, electrospun membranes made from poly(vinylidene fluoride) (PVDF) cannot meet these requirements, failing to remove oil droplets from a stable oil/water emulsion. By doping with a certain polyamide 6 solution, surface hydrophilicity, and interconnected pores with submicron size are successfully achieved. As a result, separation of a stable emulsion with an efficiency above 99% is exhibited by the modified PVDF membranes. Moreover, underwater oleophobicity of the modified PVDF membranes imparts them with good antifouling performance. The modified PVDF membranes could have great potentials in practical stable oil/water emulsion separation. (C) 2017 Wiley Periodicals, Inc.