Electrospinning is one of the techniques to produce structured polymeric fibers in the micro or nano scale and to generate novel materials for biomedical proposes. Electrospinning versatility provides fibers that could support different surgical and rehabilitation treatments. However, its diversity in equipment assembly, polymeric materials, and functional molecules to be incorporated in fibers result in profusion of recent biomaterials that are not fully explored, even though the recognized relevance of the technique. The present article describes the main electrospun polymeric materials used in oral applications, and the main aspects and parameters of the technique. Natural and synthetic polymers, blends, and composites were identified from the available literature and recent developments. Main applications of electrospun fibers were focused on drug delivery systems, tissue regeneration, and material reinforcement or modification, although studies require further investigation in order to enable direct use in human. Current and potential usages as biomaterials for oral applications must motivate the development in the use of electrospinning as an efficient method to produce highly innovative biomaterials, over the next few years.