Abstract: Capacitive deionization (CDI) has rapidly become a promising approach for water desalination. The technique removes salt from water by applying an electric potential between two porous electrodes to cause adsorption of charged species on the electrode surfaces. The nature of CDI favors the use of nanostructured porous carbon materials with high specific surface areas and appropriate surface functional groups. Electrospun carbon nanofibers (CNFs) are ideal as they have a high specific surface area and surface characteristics for doping/grafting with electroactive agents. Compared with powdered materials, CNF electrodes are free-standing and don’t require binders that increase resistivity. CNFs with an appropriate distribution of mesopores and micropores have better desalination performance. Compositing CNFs with faradaic materials improve ion storage by adding pseudocapacitance to the electric double layer capacitance. The use of electrospun CNFs as electrodes for CDI is summarized with emphasis on the major precursor materials used in their preparation and structure modification, and their relations to the performance in salt electrosorption.