Mesoporous silica materials (SBA-15 and MCF) were used as catalytic supports for the deposition of aggregated alumina species using the method consisting of the following steps: (i) anchoring 3(mercaptopropyl)trimethoxysilane (MPTMS) on the silica surface followed by (ii) oxidation of -SH to -SO3H groups and then (iii) deposition of aluminum Keggin oligocations by ion-exchange method and (iv) calcination. The obtained samples were tested as catalysts for synthesis of dimethyl ether from methanol. The modified silicas were characterized with respect to the ordering of their porous structure (XRD), textural properties (BET), chemical composition (EDS, CHNS), structure (Al-27 NMR, FUR) and location of alumina species (EDX-TEM), surface acidity (NH3-TPD, Py-FTIR) and thermal stability (TGA). The obtained materials were found to be active and selective catalysts for methanol dehydration to dimethyl ether (DME) in the MTD process (methanol-to-dimethyl ether). (C) 2015 Elsevier Ltd. All rights reserved.