Saline water electrolysis is an electrochemical process to produce valued chemicals by applying electric power. Perfluorinated sulfonic acid (PFSA) ionomers have been used as polymer electrolyte membrane (PEM) materials owing to their high sodium ion selectivity and barrier properties. However, sulfonic acid groups in PFSA ionomers are chemically decomposed under a basic catholyte condition, which makes the PEM materials lose their ionic selectivity and Faraday efficiency. In this study, double layered membranes were prepared by anchoring cross-linked hydrocarbon ionomers, as a protection layer to catholyte atmosphere, into the water channels, particularly, located at around the surface of a PFSA membrane. Here, each monomer results in the identical chemical architecture and different free volume content when polymerized.