The Chlor-alkali (CA) membrane cell is a major electrolysis system to produce valued chemicals such as chlorine gas and sodium hydroxide. The CA membrane process has been attracted in the industries, since it has relatively low energy consumption when compared with other CA processes. The key component in CA process is perfluorinated sulfonic acid ionomer membranes, which provide ion-selectivity and barrier properties to produced gases. Unfortunately, there is limited information to determine which factors should be satisfied for CA applications. In this study, the influences of PFSA membranes on CA performances are disclosed. They include ion transport behaviors, gas evolution capability, and chemical/electrochemical resistances under CA operation conditions.