A superhydrophobic-superoleophilic PVDF membrane is fabricated via an inert solvent-induced phase inversion for effective separation of both micrometer and nanometer-sized surfactant-free and surfactant-stabilized water-in-oil emulsions solely driven by gravity, with high separation efficiency (oil purity in filtrate after separation > 99.95 wt%) and high flux, which is several times higher than those of commercial filtration membranes and reported materials with similar permeation properties.