The mechanism of CN cross‐coupling reactions catalyzed by CuI associated to a 1,3‐diketonate ligand L− is investigated by cyclic voltammetry and 1H NMR spectroscopy up to the formation of the key anionic complex [LCuINHCy]−. Its reaction with PhI, shown experimentally, proceeds via an unusual iodide activation, and the transition states are investigated by density functional calculations.