Superhydrophobic and superoleophilic functionalized electrospun poly(vinylidene fluoride) (PVDF) membranes with water repellence, breathability, and oil‐sorption and oil–water separation properties were achieved with a combination of an electrospinning technique and the chemical vapor deposition of dichlorodimethyl silane. The samples were laterally characterized by scanning electron microscopy, atomic force microscopy, water contact angle measurement, and Fourier transform infrared spectroscopy. The maximum water contact angle value was 152.0 ± 2.5° for the PVDF nanofibrous membranes with 500 μL of deposited silane (PMS2) obtained under certain conditions. The PMS2 membranes showed 100.0, 93.7, 23.3, 35.0, and 100.0% separation efficiencies for n‐hexane, kerosene, crude oil, frying oil, and toluene, respectively. The understudy membrane exhibited reasonable waterproofness and remarkable breathability (water vapor transition rate = 215.21 g/m2.h). Moreover, the superhydrophobic and superoleophilic nanofibrous membranes also showed good reusability, stability, moderate water‐repellent properties, breathability, antifouling properties, and oil–water separation ability after several cycles. These properties confirmed potential in feasible applications, including protective cloths and in the purification of oil‐polluted water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47621.