Poly(vinylidene fluoride) (PVDF) membranes were prepared by non-solvent induced phase separation (NIPS) method using N N-dimethylacetamide (DMAc) as solvent dioctyl phthalate (DOP) and dibutyl phthalate (DBP) as ester additives. The morphology and structure of PVDF membrane were analyzed and discussed by scanning electron microscopy and membrane pore size analyzer. The effect of different mass ratio of DOP/DBP on the structure and properties of PVDF membranes was studied. When m(DOP)/m(DBP)=2/1, the water contact angle of the prepared PVDF membrane is 112.2° and the oil-water contact angle is 142.4°, and the kerosene droplets could completely infiltrate the membrane surface within 1231.8 ms, indicating that the membrane has the excellent super-hydrophilic oil and hydrophobicity. Furthermore, the pure oil flux is up to 945.9 L/(m2·h) and separation efficiency of water-in-oil emulsion is up to 99.3%. Therefore, it would have broad application prospects in the treatment of oil-water separation.