Sulfonated poly(ether ether ketone) (SPEEK)-silica membranes doped with phosphotungstic acid (PWA) are presented. The silica is generated in situ via the water free sol-gel process of polyethoxysiloxane (PEOS), a liquid hyperbranched inorganic polymer of low viscosity. At 100 degrees C and 90% RH the membrane prepared with PEOS (silica content = 20 wt%) shows two times higher conductivity than the pure SPEEK. The addition of small amounts of PWA (2wt% of the total solid content) introduced in the early stage of membrane preparation brings to a further increase in conductivity (more than three times the pure SPEEK). During membrane formation PWA and the sulfonic acid groups of SPEEK act as catalysts in the conversion of PECS in silica. Once the membranes are formed, PWA is incorporated in the silica network and acts as proton conductivity enhancer. The correlation between morphology and proton conductivity allows establishing the optimal doping level and preparation procedure. The morphology is studied by transmission electron microscopy (TEM) while the proton conductivity is measured by impedance spectroscopy (IS). The direct methanol fuel cell performance is also investigated. (C) 2008 Elsevier B.V. All rights reserved.