The cyclopentadienyl (Cp) group is avery important ligand for many transition-metal complexes which have been applied in catalysis.The availability of chiral cyclopentadienyl ligands (Cp x )lags behind other ligand classes,thus hampering the investigation of enantioselective processes.W er eport al ibrary of chiral Cp x Ir III complexes equipped with an atropchiral Cp scaffold. Ar obust complexation procedure reliably provides Cp x Ir III complexes with tunable counterions. In aproof-of-concept application, the iodide-bearing members are shown to be highly selective for enyne cycloisomerization reactions.The dehydropiperidine-fused cyclopropane products are formed in good yields and enantioselectivities.