Nanotechnology is one of the rapidly growing scientific disciplines due to its enormous potential in creating novel materials that have advanced applications. Electrospinning has been found to be a viable technique to produce materials in nanofiber form. Ferroelectric and/or piezoelectric materials in nanofiber and/or nanowire form have been utilized for producing energy harvesting devices, high frequency transducers, implanted biosensors, vibration absorbers and composite force sensors, etc. An in-depth review of research activities on the development of ferroelectric nanofibers, fundamental understanding of the electrospinning process, and properties of nanostructured fibrous materials and their applications is provided in this article. A detailed account on the type of fibers that have been electrospun and their characteristics is also elaborated. It is hoped that the overview article will serve as a good reference tool for nanoscience researchers in ferroelectric materials.