Proton-exchanged montmorillonite showed catalytic activity for intermolecular allylsilylation, arylsilylation, and terminal silylation of alkynes with allylsilanes. The reaction selectivity greatly depended on the solvent used. Reactions proceeded with various terminal alkynes and allylsilanes in good to moderate yields. The reaction pathways involving cationic Si species on the montmorillonite surface were also investigated. (C) 2011 Elsevier Ltd. All rights reserved.