Friedel-Crafts acylation of aromatic ethers with acid anhydrides in the presence of mesoporous material, cation-exchanged K10 montmorillonite (Mn+ - mont., where Mn+=Fe3+, Zn2+, Cu2+, Al3+ and Co2+) was investigated. Fe3+- and Zn2+-exchanged montmorillonites displayed higher activities ascribed to the synergistic effect of Bronsted and Lewis acidities. Selective acylation is a significant achievement with the formation of 1-acyl-2-methoxynaphthalene, 4-acyl anisole and 4-acyl veratrole from respective aromatic ethers.