Perfluorinated sulfonic acid (PFSA) ionomers have been widely used as representative polymer electrolyte membrane (PEM) materials for water electrolysis to generate hydrogen and oxygen gases with a high purity (e.g., 99.999%) simultaneously. PEM should satisfy high selectivity of proton to water and act as gas barrier to hydrogen and oxygen in order to improve current efficiency which is a barometer to determine how effectively the electric energy is used for water electrolysis. In this study, PFSA ionomers with different chemical architectures and equivalent weights were used to make PEM materials for water electrolysis. The structure-property-performance relationship was systematically investigated.