Two alkoxysilyl-modified ionic liquids (ILs) have been synthesized and further grafted onto mesoporous silica, MCM-41; these ionic liquids were used for dispersing AuCl₃ catalysts that activate C–H bonds as required for the synthesis of propargylamines by coupling alkyne, aldehyde and amine (A³ coupling) species. ²⁹Si NMR experiments demonstrate the formation of covalent bonds between alkoxysilyl-modified Bmim IL and the MCM-41 surface through silanol groups. The catalytic activities of Au(III)-supported MCM-41 and Au(III) homogeneous catalysts are lower than those obtained for the IL functionalized Au–MCM-41 solids when the same gold loading is considered. An interaction between Au(III) species and the IL is proposed for explaining the stabilization of gold(III) species. However, successive reaction cycles result in a decrease in the catalytic activity that has been explained on the basis of gold leaching.