Herein, we demonstrate that the use of N-heterocyclic carbene (NHC) ligands enables chemodivergent SM coupling of chloroaryl triflates. A Pd/SIPr precatalyst provides selective reaction at chloride, while a Pd/SIMes precatalyst favors reaction at triflate. In contrast to the limited scope reported for the prior phosphine ligand-controlled method,4,7this NHC ligand-controlled SM coupling is general to a variety of chloroaryl triflates and arylboronic acids.