A worldwide steady increase in oily wastewater, due to oil spillage and various industrial discharges, requires immediate efforts toward development of an effective strategy and materials to preserve the natural water bodies. Designing a superwettable fibrous membrane of robust structure and anti-fouling property for efficient separation of oil-water mixtures and emulsions is therefore highly demanding. The electrospun fibrous membrane, which possesses porosity and flexibility and properties including superwettability and tunable functionality, can be considered as apposite materials for this cause. In this approach, we combined two strategies, viz., Pickering emulsion and near gel resin (nGR) emulsion electrospinning together to produce a fibrous nanocomposite membrane for efficient oil−water separation and demulsification. nGR Pickering emulsions were stabilized using hydrophilic SiO 2 nanoparticles and successfully optimized for fabricating the crosslinked core sheath-structured fibrous membrane. The prepared membrane provided twofold functionality due to the core sheath structure of the fibers. The crosslinked polystyrene core offered high oil adsorption capacity, whereas SiO 2 -functionalized crosslinked polyvinyl alcohol sheath provided a rough, superhydrophilic surface with underwater oleophobic behavior to the membrane. The optimized SiO 2 -Pickering emulsion-templated nanocomposite membrane demonstrated excellent underwater anti-oil adhesion behavior (UWOCA ∼148°) with efficient oil−water separation capacity of more than 99% and separation flux up to 3346 ± 91 L m −2 h −1 . The membrane was evaluated against various oil−water emulsions and found to have a superior separation efficiency. Moreover, excellent anti-oil adhesion property provided the intact membrane, where consistent separation performance was achieved up to 10 separation cycles without any loss. The membrane was used for separation of hot oil−water emulsions and showed no structural disintegration or loss in separation performance when exposed to elevated temperatures. The developed nanocomposite membranes could efficiently be used for separation and demulsification, and their applications can be explored in various other fields including selective sorption, catalysis, and storage in future.