Due to increasing of oil spills and high organic contamination of marine environment, developing of cog-effective and rapid oil/water separation technique has become inevitable. Herein, freestanding and flexible hybrid polystyrene nanofibers are introduced as highly efficient hybrid membrane for ultrafast oil/water separation without external pressure. Typically, different loading of Fe3O4 nanoparticles embedded into polystyrene nanofibers using electrospinning to fabricate superhydrophobic/super-oleophilic membrane. The morphological shape, crystal structure and surface wettability behavior were elucidated by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and contact angel, respectively. The optimum loading of magnetite nanoparticles into the nanofiber membranes was investigated to achieve best separation performance. The obtained results demonstrated that the incorporation of (Fe3O4) nanoparticles into membrane has a significant impact for enhancing superhydrophobic properties and the separation efficiency against light and heavy oils. Among all formulations, the fabricated (PS@Fe(3)O(4)10 wt.%) membrane revealed ultrahigh flux (5000 L m(-2 )h(-1)) with separation efficiency of 99.8 % for hexane under gravity driven process and excellent superhydrophobicity with water contact angle 162 degrees moreover excellent reusability 98.5 % for 50 consecutive cycles. Interestingly, the proposed hybrid nanofiber membrane achieved distinct separation efficiencies 95 % and 92 % for food oils such as olive oil and sesame oil. Overall, the current study provides cost-effective and facile approach to distinctly improve the membrane performance for durable oil/water separation technique.