The present article includes the synthesis of nanophase-separated poly (arylene ether) multiblock copolymers. A series of poly (arylene ether sulfone) hydrophobic oligomers consisting of bisphenol-A groups were reacted with a disulfonated poly (arylene ether ketone) hydrophilic oligomer containing 4, 4'-bis (4-hydroxyphenyl)valeric acid moieties to prepare multiblock copolymers. The synthesized oligomers and block copolymers were characterized by using FT-IR,1H NMR spectra and Gel Permeation Chromatography. The membranes obtained by solution casting method exhibited good dimensional and thermal stability. The increase in hydrophobic block length reduced the water uptake and methanol permeability of the membranes. The complexation of multiblock copolymer with ionic liquid (1-butyl-3-methyl-imidazolium tetrafluoroborate) resulted into novel hybrid membranes. These showed enhanced proton conductivity without affecting the mechanical stability. The Fenton's test revealed that the hybrid multiblock membranes were stable towards radical oxidation. The hydrophobic-hydrophilic phase separation was characterized by using tapping mode Atomic Force Microscopy (AFM). The hybrid membranes showed better fuel cell performance than that of pristine membrane. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.