Iridium complexes show high catalytic activity in intermolecular additions of acid chlorides to terminal alkynes to afford valuable (Z)-beta-chloro-alpha,beta-unsaturated ketones. Ligands in the catalytic system play a crucial role in this reaction. An N-heterocyclic carbene (NHC) is an efficient ligand for the addition of aroyl chlorides, while dicyclohexyl(2-methylphenyl)phosphine (PCy2(o-Tol)) is indispensable for the reaction of aliphatic acid chlorides. The addition reactions proceed regio- and stereoselectively with suppression of decarbonylation and beta-hydrogen elimination, which have been two major intrinsic problems reactions. Stoichiometric reactions of active iridium catalysts with aroyl chlorides and aliphatic acid chlorides are carried out to gain insights into the reaction mechanisms. in transition-metal-catalyzed reactions. Stoichiometric reactions of active iridium catalysts with aroyl chlorides and aliphatic acid chlorides are carried out to gain insights into the reaction mechanisms.