In this work, the oil-water separation performance of a novel electropsun nanofibrous polystyrene (PS) membrane is reported. The new claim is based on imposing microporosity feature on the fibers surface using a pore-forming agent. Polystyrene, Dimethylacetamide as solvent and Tetraethylammonium chloride as salt additive were used for preparing the dope solution for electrospinning. Different amounts of Polyvinylpyrrolidone (PVP; 0, 1.5, 3, 5 and 7 wt.%) were also added to the dope solution, as pore-forming agent. The electrospuned samples then soaked in the deionized water for 2 and 7 days, respectively, to prepare electrospun PS membranes with microporous structure on the fibers’ surface. All samples were characterized using FE-SEM and static contact angle methods. Oil sorption experiments were conducted using Kerosene-water emulsion. Morphological observations revealed that fibers’ diameter increased at higher PVP concentrations (>3 wt.%). The lowest surface wrinkle feature was observed for the sample contains 1.5 wt.% PVP. On the other hand, higher fibers’ surface microporosity could be observed by increasing PVP concentration. Moreover, static surface CA was measured for the samples containing 0, 1.5, 3, 5 and 7 wt% PVP. In better words, the surface heterogeneity is increased at higher PVP concentration in dope solution. This can be concluded by this fact that with increase the PVP concentration the surface porosity of fibers increased when they are soaked in water. Soaking in water bath can dissolve the PVP from the fibers surface and leaves a microporous structure on the body. This led to increase the roughness and the specific surface, as well. Furthermore, the oil sorption capacity increased with increase in the fibers’ surface microporosity, significantly, and the highest one measured at 28 g/g for the sample with 3 wt. % PVP concentration in the dope solution. Such Such superoleophilicity behavior plays a critical role in oil-water separation. Results in