Saline water electrolysis is a representative electrochemical conversion to produce chlorine gas and sodium hydroxide as major products by applying electric power. Perfluorinated sulfonic acid (PFSA) ionomers have been usually used as polymer electrolyte membrane materials owing to high sodium ion selectivity and strong resistance to acidic compounds (e.g., Cl2, HCl and so on) produced in anode. However, PFSA ionomers have been suffering from chemical degradation occurring when exposed under harsh basic condition in cathode. In this study, double layered chlor-alkali membranes were prepared by anchoring crosslinked hydrocarbon ionomer via radical polymerization technique in water channels located in a surface layer of PFSA ionomer membranes and electrochemically evaluated.