The benzylation of benzene and substituted benzenes reaction employing benzyl chloride as the alkylating agent over a series of gallium-containing mesoporous silicas with different Ga contents has been investigated. These materials (Ga-HMS-n) have been characterized by chemical analysis, BET and XRD. The mesoporous gallium-containing materials showed both high activity and high selectivity for benzylation of benzene. The activity of these catalysts for the benzylation of different aromatic compounds is in the following order: benzene > toluene > p-xylene > anisole. Kinetics of the benzene benzylation over these catalysts have also been investigated. (c) 2006 Elsevier B.V. All rights reserved.