Perfluorinated sulfonic acid (PFSA) ionomers have been commonly used as representative polymer electrolyte membrane (PEM) materials for fuel cell electric vehicles owing to their fast proton transport and excellent chemical resistance. However, PFSA materials still have weakness associated with chemical degradation occurring as a result from radical attacks, which induce membrane thickness reduction, leading to hydrogen crossover, and/or reduced electrochemical performances. In this study, cerium derivative radical scavengers were designed as functional additives to enhance the chemical durability of PFSA PEM. Their optimum content was suggested, comprehensively considering their radical resistance as well as other fundamental characteristics associated with long-term durability and electrochemical performance.