A derivative of polyetheretherketone (PEEK) having sulfonic acid groups and silicon-containing substituents covalently bound to the aromatic backbone has been prepared as proton-exchange membrane material. The polymer 4 (PhSiS-PEEK) has been synthesized via (i) sulfonation of PEEK up to 0.9 degree of sulfonation (DS, the number of sulfonic groups per repeat unit), (ii) conversion of sulfonated PEEK 1 (SPEEK09) into sulfonyl chlorinated derivative 2 (PEEKSO2Cl), (iii) lithiation of 2 and subsequent addition of PhSiCl3, followed by hydrolysis. The chemical structure of the synthesized polymers has been investigated by H-1 NMR and C-13 NMR and ATR/FTIR spectroscopy and their thermal stability has been evaluated by thermogravimetric analysis. The presence of inorganic moieties increases the thermal stability of 4 with respect to the sulfonated and not silylated product. Despite its very high DS, PhSiSPEEK is insoluble in water but does not possess the plastic properties needed to be used as an electrolyte membrane. Blend membranes made of SPEEK05 (DS = 0.5) and containing 10 and 25 wt % of 4 (DS = 0.9, degree of silylation DSi = 0.1) have been prepared and characterized by water uptake measurements and electrochemical impedance spectroscopy. The combination of the two functionalized polymers having different properties allows to obtain proton-conducting electrolytes that are potential candidates for fuel cells applications. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2178-2186, 2010