Wastewater containing oil/water emulsion has a serious ecological impact and threatens human health. The impact worsens as its volume increases. Oil/water emulsion needs to be treated before it is discharged or reused again for processing. A membrane-based process is considered attractive in effectively treating oil/water emulsion, but progress has been dampened by the membrane fouling issue. The objective of this study is to develop polyvinylidene fluoride (PVDF) membranes customized for oil/water emulsion separation by incorporating assembly of tannic acid (TA) and polyvinylpyrrolidone (PVP) in the polymer matrix. The results show that the assembly of TA/PVP complexation was achieved as observed from the change in colour during the phase inversion and as also proven from the characterization analyses. Incorporation of the TA/PVP assembly leads to enhanced surface hydrophilicity by lowering the contact angle from 82° to 47°. In situ assembly of the TA/PVP complex also leads to enhanced clean water permeability by a factor of four as a result of enhanced mean flow pore size from 0.2 to 0.9 µm. Owing to enhanced surface chemistry and structural advantages, the optimum hydrophilic PVDF/TA/PVP membrane poses permeability of 540.18 L/(m2 h bar) for oil/water emulsion filtration, three times higher than the pristine PVDF membrane used as the reference.