Chlor-alkali (CA) membrane process is a commercially useful process to produce valued chemicals such as chlorine, sodium hydroxide and hydrogen via salined water electrolysis using sodium ion (Na+)-selective membranes. The most important issue in CA process is to reduce high energy consumption. A plausible solution is to obtain highly Na+-conductive membranes. The representative membrane materials are chemically stable perfluorinated sulfonic acid (PFSA) ionomers such as Nafion® and Aciplex®. PFSA membranes, but it is necessary to develop alternatives to PFSA membranes. In this study, a sulfonated poly(arylene ether sulfone) copolymer membrane is radiation-grafted with a highly sulfonated poly(styrene) used as a side chain material.