This chapter summarizes some crucial parameters in preparing electrospun membranes for fuel cell applications. The electrospinning setup mainly consists of three essential parts: a high voltage supply, a steel needle with a pump, and a conductive collector. The basic operating parameters of electrospinning are discussed to gain an understanding of electrospun membranes. The effect of the operational parameters governed by the electrospinning process toward the formation of electrospun nanofibers is examined explicitly. The recent applications of electrospun membranes in fuel cells have also been discussed. Well-controlled electrospinning parameters will provide a smaller diameter of nanofibers with increasing ionic domains that will consequently promise enhanced fuel cell performance. Thus, by reviewing all the above matters, it is believed that the understanding of the electrospinning process can be a powerful platform for the fabrication of a desirable electrospun membrane that can further improve the membrane performance as a polymer electrolyte membrane. © 2023 Elsevier Inc. All rights reserved.