A series of cross-linked hybrid membranes with low water uptake, high dimensional stabilities, as well as high oxidative stabilities are prepared by a combination of silane-crosslinking and thiol-ene click chemistry based on a sulfonated poly (arylene ether ketone) (SPAEK) with propenyl groups. H-1 NMR measurement and Fourier transform infrared spectroscopy are used to characterize and confirm the chemical structure of SPAEK and its cross-linked hybrid polymer exchange membranes. We also investigate the changes in methanol permeability, proton conductivity and mechanical properties. Our findings demonstrate that the Si-O-Si cross-linked structure makes a great contribution to the improvement of dimensional and chemical stabilities. Therefore, these cross-linked hybrid membranes could be considered as promising materials for direct methanol fuel cell applications. (C) 2012 Elsevier B.V. All rights reserved.