ABSTRACT Efficient separation of emulsion mixtures is essential for eradicating oil contamination, emphasizing the need for superhydrophobic membranes. In this study, we report the fabrication of a superhydrophobic/superoleophilic (SH/SO) polystyrene (PS) nanofibrous membrane embedded with zeolitic imidazolate framework‐8 (ZIF‐8) nanoparticles for the efficient separation of water‐in‐oil emulsions and immiscible oil/water mixtures. The incorporation of ZIF‐8 imparts enhanced surface roughness, O/W separation efficiency, and excellent thermal and chemical stability to the membrane. The electrospun ZIF‐8/PS composite nanofibrous membrane demonstrates significant enhancements in permeate flux, water contact angle (WCA), absorption capacity, and separation efficiency compared to the pristine nanofibrous membrane. The composite nanofibrous membrane exhibits a WCA of approximately 155° ± 1.5°. The water‐in‐diesel emulsion achieves an oil permeate flux of 1886 ± 91 L/m 2 h, whereas the flux for immiscible diesel/water separation reaches 2936 ± 103 L/m 2 h. Furthermore, the ZIF‐8/PS composite nanofibrous membrane effectively separates oil from water/sunflower oil, water/bean oil, water/peanut oil, and water/diesel emulsions. The composite membrane achieves a separation efficiency of 99% ± 0.5% and exhibits excellent reusability and chemical stability. These attributes underscore the potential of the ZIF‐8/PS composite nanofibrous membrane for practical oil/water separation applications.