In this era of nanotechnology, electrospun nanofibrous membranes offer versatile characteristics, such as mechanical toughness and a large surface area, making them attractive for various applications. Electrospinning is an emerging methodology for producing nanofibers. Furthermore, electrospinning yields uniform pore size, which is considered a crucial characteristic of water treatment membranes. Consequently, electrospun membranes are increasingly employed in water treatment applications such as membrane distillation and pretreatment of feed prior to reverse osmosis or nanofiltration for the removal of divalent metal ions and other contaminants. This chapter addresses the optimization of process parameters and the fabrication of electrospun, nonwoven, nanofibrous membranes and modification of their surface chemistry for desalination applications. Limitations, research challenges, and future perspectives are also discussed.