Polymer electrolyte membrane fuel cells become more promising energy technology and has received extensive interest in recent years due to more benefit that it can offer compared to other fuel cell. As the heart of fuel cell system, polymer electrolyte membrane plays a vital role in determining the cell performance. However, the biggest challenge to have an excellent cell performance is to develop polymer electrolyte membrane with excellent thermal, mechanical and chemical stability as well as high conductivity and low cost. Thus, as an alternative to achieve the important properties for excellent cell performance, electrospun nanocomposite-based PEM is developed. This chapter present a comprehensive review about the electrospun nanocomposite-based polymer electrolyte membrane that has been used in fuel cell applications. The state of the art of the polymer electrolyte membrane and the challenges of the commercialization have been described. The way to develop the nanofibers materials using electrospinning technique and method to fabricate electrospun nanocomposite membrane is discussed.