Radiation-induced graft polymerization of sulfo-containing styrene derivatives into crystalline poly(ether ether ketone) (PEEK) substrates was carried out to prepare thermally and mechanically stable polymer electrolyte membranes based on an aromatic hydrocarbon polymer, so-called "super-engineering plastics". Graft polymerization of the sulfo-containing styrene, ethyl 4-styrenesulfonate (E4S) into a high crystalline PEEK substrate (degree of crystallinity: 32%) hardly progressed, whereas graft polymerization into a low crystalline PEEK substrate (degree of crystallinity: 11%) gradually progressed, achieving a grafting degree of more than 50% after 72 h. Oxygen radicals appeared in the ESR spectra of irradiated PEEK films, indicating that graft polymerization initiates from the phenoxy radicals generated by scission of PEEK main chains and proceeds so as to yield block type grafts. The PEEK-based polymer electrolyte membrane (PEM) converted by aqueous hydrolysis of grafted films exhibited mechanical strength (100 MPa), being 88% of the original PEEK substrates. These mechanical properties of PEEK-based PEM are much higher than those of graft-type fluorinated PEM reported previously and almost three times higher than that of Nafion (35 MPa). Wide- and small-angle X-ray scattering (WAXS and SAXS) indicated that the graft polymerization was accompanied with recrystallization of the amorphous phase of PEEK substrate, the well known solvent-induced recrystallization of amorphous PEEK solids, to form a weak lamellar structure with 8 nm spacing. Complementary SAXS and small-angle neutron scattering (SANS) observations clearly showed that the graft-type PEEK membranes possessed ion channel domains with the average distance of 13 nm, being larger than that of Nafion. Furthermore, there was a micro-structure in the ion channels with the average distance of 1.8 nm. (C) 2010 Elsevier Ltd. All rights reserved.