This paper reports on the preparation and characterization of sulfonated poly(ether ether ketone) (sPEEK)-based mixed matrix membranes. The inorganic matrix consisted of silica: Aerosil (R) 380, tetraethoxysilane (TEOS) or a combination of both to obtain an interconnected silica network. The behavior of these membranes in ethanol-water systems was studied for application in a direct ethanol fuel cell (DEFC). Uptake measurements showed that the converted TEOS content had a strong influence on the hydrophilicity of the membranes. Proton conductivity was strongly related to the water content in the membrane, but the proton diffusion coefficients of membranes with various Aerosil (R) 380-TEOS combinations were similar. Dynamic measurements in liquid-liquid (L-L) and liquid-gas (L-G) systems were performed to study the ethanol transport through the membrane. No reduction in ethanol permeability was obtained in the L-L system, but a remarkable reduction was obtained in the L-G system when 2 M ethanol was applied. The reinforcing characteristic of the combined Aerosil (R) 380-TEOS-system were best observed at 40 degrees C with 4 M ethanol. The fuel cell performance prediction based on the selectivity of proton diffusion coefficient to ethanol permeability coefficient showed for nearly all composite membranes an improvement with respect to the polymeric reference. The presence of an inorganic phase led to relatively constant proton diffusion coefficients and lower ethanol permeability coefficients in comparison with the polymeric reference. (C) 2009 Elsevier B.V. All rights reserved.