The proton exchange membrane fuel cells(PEMFCs) have been noticed as the promising power sources. One of the important components in PEMFC is the proton exchange membranes(PEMs). Recently various materials for PEMs have been investigated for fuel cell applications. Sulfonated aromatic hydrocarbon-based multiblock copolymers have drawn much interest due to their well-defined phase separation between hydrophilic and hydrophobic blocks. In our group, multiblock copolymers based on highly sulfonated poly(fluorenyl ether sulfone)s were developed as highly conductive and stable polymer electrolyte membranes. We report herein the investigation of the influence of phase separation and properties by block length of the corresponding membranes.