Innovation and optimization have shifted battery technologies beyond the use of lithium ions and fostered the demand for enhanced materials, which are vital factors determining the energy, power, durability, and safety of systems. Current battery materials vary in their sizes, shapes, and morphology, and these have yet to meet the performance standards necessary to prevent deterioration in regard to the efficiency and reliability of beyond-lithium technologies. As a versatile and feasible technique for producing ultrathin fibers, electrospinning has been extensively developed to fabricate and engineer nanofibers of functional materials for battery applications. In this review, the basic concepts and characteristics of beyond-lithium batteries are expounded, and the fundamentals of electrospinning are reviewed. The aim is to provide a guide to researchers going into this field. Focuses are placed on how electrospinning can address some of the key technical challenges facing beyond-lithium technologies. We hope the knowledge presented in this work will stimulate the design of electrospun materials for future battery applications.