Poly(arylene ether sulfone) multiblock copoly. were synthesized via oligomeric sulfonation. The successful oligomeric sulfonation enabled multiblock copolymer membranes with different hydrophobic block moiety (biphenyl and naphthalene units). High local concentration of sulfonic acid groups within the hydrophilic blocks enhanced the phase separation between hydrophilic and hydrophobic moiety. Rigid, nonpolar, and planar hydrophobic moiety such as naphthalene groups were effective in increasing proton conductivity and decreasing gas permeability. The multiblock copolymers with naphthalene hydrophobic units with IEC = 2.01 mequiv/g showed comparable proton conductivity to Nafion NRE 212 membrane (0.91 mequiv/g) at >40% RH. The longer blocks were found to increase a characteristic factor (ratio of the proton conductivity to the water volume fraction) as well as phase separation. The membrane showed relatively low oxidative stability under Fenton's test conditions due to higher water uptake and swelling. However, low gas permeability could compensate this drawback for fuel cell applications.