Electrodialysis process with bipolar membrane is economically very attractive and has a multitude of interesting potential applications. Although the process expand applications such as waste water treatment, and recovery of pure organic and inorganic acids with the efficient bipolar membrane, the large scale utilization of bipolar membrane is still limited by unsatisfactory membrane properties and by a lack of application knowhow. In this study, the block copolymer(BPSf) was prepared by copolymerization of polysulfone(PSf) and poly(phenylene sulfide sulfone)(PPSS). The cation exchange membranes were prepared by the sulfonation of BPSf with chlorosulfonic acid and the anion exchange membranes were prepared by the chloromethylation by chloromethyl ether and the amination by triethyl amine. The bipolar membranes were fabricated by stacking anion exchange membrane over cation one with the conditions of good electrochemical characteristics and physical properties. The influence of intermediate layer components on the bipolar membrane properties such as current-voltage curve and pH was investigated, and the components were varied by pasting non-woven cloth, various polymers, and amine groups. Among the various bipolar membranes, the membranes prepared by tertiary amine group exhibited the best water-splitting effect and 2.4 V of membrane potential at 100 mA/cm(2) of current density.