Although the versatilities of zeolitic materials are widely known to chemists and materials scientists, their exclusive microporosity sometimes causes various defections especially in the diffusion of reactant and product molecules in catalytic reactions. Silica–alumina/epoxy-resin composite materials were obtained from TMOS (tetramethoxysilane), aluminum acetylacetonate and bisphenol A diglycidyl ether with a cyclic acid anhydride as both condensation and curing reagents. Hydrothermal treatment of the composite materials with TPAOH (tetra- n-propylammonium hydroxide) crystallized the amorphous silica–alumina part to the MFI zeolite crystalline phase and induced the phase separation of epoxy-resin domain from the zeolite phase at the same time, forming both zeolite microporosity and mesoporosity in the solid catalyst after calcination. The mesoporous MFI zeolite thus prepared had a good catalytic activity in liquid phase Friedel–Crafts benzylation reaction. The mesoporous channels fabricated in the MFI zeolite material enhanced the diffusion of reactants and products in the solid matrix, and thus it showed a better catalytic activity in the benzylation of toluene together with the high selectivity of the mono-substituted para-isomer. The new methodology reported in this paper to produce the mesoporous zeolite materials will promote the chemistry and the applications of zeolite catalysts and related materials.