Offshore oil spills, industrial oily wastewater, and domestic oil pollution are some of the most serious global challenges and are leading environmental causes of morbidity and mortality. The development of effective methods to separate oils from water surfaces and oil/water mixtures is thus crucial. Electrospinning is a unique technique to produce nonwoven membranes formed by fine submicrometric fibers from polymer solution or melt through the application of high electrostatic forces. Electrospun nanofibrous membranes are considered a promising candidate for oil/water separation, with competitive advantages including a large specific surface area, high porosity, good pore channel connectivity, facile tunability of surface wettability, and easily scalable fabrication from various materials.