Water purification and water desalination via membrane technology are generally deemed as reliable supplementaries for abundant potable water. Electrospun nanofiber-based membranes (ENMs), benefitting from characteristics such as a higher specific surface area, higher porosity, lower thickness, and possession of attracted broad attention, has allowed it to evolve into a promising candidate rapidly. Here, great attention is placed on the current status of ENMs with two categories according to the roles of electrospun nanofiber layers: (i) nanofiber layer serving as a selective layer, (ii) nanofiber layer serving as supporting substrate. For the nanofiber layer’s role as a selective layer, this work presents the structures and properties of conventional ENMs and mixed matrix ENMs. Fabricating parameters and adjusting approaches such as polymer and cosolvent, inorganic and organic incorporation and surface modification are demonstrated in detail. It is crucial to have a matched selective layer for nanofiber layers acting as a supporting layer. The various selective layers fabricated on the nanofiber layer are put forward in this paper. The fabrication approaches include inorganic deposition, polymer coating, and interfacial polymerization. Lastly, future perspectives and the main challenges in the field concerning the use of ENMs for water treatment are discussed. It is expected that the progress of ENMs will promote the prosperity and utilization of various industries such as water treatment, environmental protection, healthcare, and energy storage.