In consideration that a high tensile strength and ion exchange capacity are maintained as the swℓing of membrane is controlled by the coagulation of PSf with the introduction of ion exchange groups and PPSS without the introduction of ion exchange groups, the block copolymer of PSf and PPSS were synthesized. The cation exchange membrane was prepared by sulfonation with CSA and casted. The synthesized block copolymer and cation exchange membrane were characterized by FT-IR and their thermal stability was confirmed by TGA. The optimum sulfonation could be accomplished at a mole ratio of BPSf to CSA 1:3. The best electrochemical properties obtained by the optimal condition were area resistance of 4.37 Ωㆍtextrmcm2, ion exchange capacity of 1.71 meq/g dry membrane, water content of 0.2941 g H2O/g dry membrane, and fixed ion concentration of 5.81 meq/g H2O. When GBL was used as an additive, area resistance was increased by 13.7 % and ion exchange capacity was increased by 14.6%. When the membrane was fabricated in a form of composite using non woven cloth as a support. the tensile strength of membrane could be improved, but the electrochemical characteristics were not influenced.