Graft copolymers with ionic backbones and hydrophobic fluorinated side chains have been prepared by using lithiated poly(2,6-dimethy1-1,4-phenylene oxide) (PPO) as a macroinitiator for anionic polymerization of 4-fluorostyrene. After grafting of the poly(4-fluorostyrene) (PI'S) side chains, the PPO backbone was selectively sulfonated using trimethylsilylchlorosulfonate under mild and controlled conditions. Microscopy of solvent cast membranes revealed copolymer self-assembly into remarkably regular and well-ordered morphologies which, depending on the molecular structure, included lamellar and cylindrical arrangements of the proton conducting ionic nanophascs. Thermal analysis indicated separate glass transitions of the PFS and PPO phases, and high thermal degradation temperatures of the membrane at approximately 220 and 300 degrees C for the H+ and the Na+ forms, respectively. The proton conductivity of fully hydrated acidic membranes was similar to that of Nafion, reaching above 0.2 S cm(-1) at 120 degrees C. Compared at the same ion exchange capacity, the proton conductivity of the graft copolymer membranes was two times higher than that of a membrane based on an ungrafted sulfonated PPO. The study showed that it is possible to tailor and prepare proton-exchange membranes with well-ordered morphologies and high proton conductivity by employing graft copolymers with a sulfonated backbone bearing hydrophobic side chains.