Electrospinning is a unique and versatile technique to produce fine submicrometric fibers and nanofibrous membranes from polymer solution or melt. In the last decade, fluorinated polymers (particularly polyvinylidene fluoride, PVDF, VDF copolymers and polytetrafluoroethylene, PTFE) have attracted significant attention in electrospinning processes. Fluoropolymers are extraordinary specialty materials characterized by outstanding properties, such as high chemical resistance, high thermostability, low surface energy, and electroactivity. Interestingly, electrospinning can further maximize their properties, thus allowing to fabricate advanced and fascinating nanostructured materials. Electrospun fluoropolymers show a tremendous potential for exciting applications in several areas, from filtration to environmental and energy fields (e.g. Li-ion batteries), chemical and biological sensing, electroactive applications, superhydrophobic coatings, textile and sport wear, and biomedical applications. This review presents the recent advances in the use of the wide family of fluoropolymers in electrospinning, describing the processes for the preparation of the fibrous materials, their properties, and their applications in several fields.