The fuel cell application is an imperative energy conversion transformation with impressive potential for Malaysian future vitality. The relatively small market of fuel cell technology in Malaysia, causing considerable development in the domestic market, should be created to ensure a noteworthy contribution to Malaysia’s energy industry. Currently, the research towards advanced polymer electrolyte membranes that can provide high proton conductivity and good durability is actively being studied. This article reviews the promising properties of polyphenylsulfone (PPSU) polymer materials as proton exchange membranes. This alternative polymer material would be best to replace the costly and counter the drawbacks of the perfluorinated membranes in fuel cell systems. Unfortunately, the interconnected hydrophilic channels of PPSU polymers are not well developed as the Nafion membrane. Thus, the PPSU was modified by a sulfonation reaction to confer their protonic conduction properties. In addition, the modification of the highly sulfonated PPSU by thermal crosslinking as a potential technique to improve the mechanical and chemical durability of the PPSU was discussed. Further, the effect of mixing various additives to develop the PPSU nanocomposite membrane on proton conductivity, physicochemical properties, mechanical properties and fuel cell performance are also discussed in this work.