Proton exchange membrane (PEM) is pivotal for proton exchange membrane fuel cells (PEMFCs). In the present work, a block copolymer with hydrophilic alkyl sulfonated side groups and hydrophobic flexible alkyl ether side groups, poly(5'-hexyloxy-1',4-biphenyl)-b-poly(2',4'-bispropoxysulfonate-1',4-biphenyl) (HBP-b-xBPSBP), is designed and synthesized by copolymerization of the hydrophilic and hydrophobic oligomers. The oligomers are synthesized via a Pd-catalyzed Suzuki cross-coupling of 1,3-dibromo-5-hexyloxybenzene, and 3,3'-[(4,6-dibromo-1,3phenylene)bis(oxy)]bis(propane-1-sulfonate) or 1,4-bis(4,4,5,5tetramethyl-1,3,2-dioxaborolan-2-yl)benzene. The good solubility and film-forming characteristics are achieved via the introduction of flexible hexyloxy side groups, and high ion exchange capacity (IEC) is achieved via the introduction of high density of alkyl sulfonated side groups. The HBP-b-0.5BPSBP has the highest IEC of 3.17 mmol/g, the highest proton conductivity of 43.5 mS/cm at 95 °C and 90% relative humidity (RH) and low methanol permeability of 6.45 × 10 À 7 cm 2 /s. Meanwhile, crosslinked HBP-b-xBPSBP exhibits promising water uptake, swelling ratio and low methanol permeability. These characteristics are attributed to the crosslinked structure and the hydrophilic/hydrophobic nanophase separation morphology promoted by the poly(mphenylene) main chains, flexible alkyl ether groups, and alkyl sulfonated side groups.