ZnCl2-aluminosilicate catalysts were prepared via a sol-gel route involving fluoride-catalyzed hydrolysis of aluminum and silicon alkoxides in the presence of NaF, KF, NH4F and ZnF2. The catalysts were characterized by employing Si-29, Al-27 and F-19 solid-state MAS NMR. The dependence of the activities of the catalysts on the nature and amount of fluoride present in the catalysts were investigated using Friedel-Crafts alkylation reaction of benzene with benzyl chloride.