The iridium-based catalytic system, [{Ir(μ-Cl)(CO) 2 } 2 ]/NEt(i-Pr) 2 , was examined in the coupling reaction of iodotrisubstituted silanes (R 3 SiI) with various terminal arylalkynes (R 1 C CH). Under optimum conditions, the process occurs very efficiently (in particular for Me 3 SiI and Me 2 PhSiI), giving exclusively the respective C sp -silyl functionalized alkynes (R 1 C CSiR 3 ). Additionally, this iridium-based catalytic system was successfully used for the preparation ...