A series of organic silica/Nafion composite membranes has been prepared by using organic silane coupling agents (SCA) bearing different hydrophilic functional groups. The physico-chemical properties of the composite membranes have been characterized by electrochemical techniques, scanning electron microscopy (SEM), diffuse-reflection Fourier-transform infrared spectroscopy (DRFTIR), wide-angle Xray diffraction (WAXRD), thermogravimetric analysis (TGA), and thermogravimetric mass spectrometry (TG-MS). It has been found that some organic silica/Nafion composite membranes modified by organic silane agents bearing amino groups exhibit extremely low methanol crossover and proton conductivity values, e.g., a composite membrane shows a proton conductivity that is about five orders of magnitude lower and a methanol permeability that is about three orders of magnitude lower than those of a Nafion 117 membrane. However, under optimized conditions for controlling the basicity of the amino groups, we also obtained a composite membrane with 89% lower methanol permeability and 49% lower proton conductivity compared with Nafion] 17 membrane. The results clearly demonstrate that the diffusion of methanol and protons through the membrane can be controlled by adjusting the functional groups on the organic silica. (C) 2008 Elsevier B.V. All rights reserved.