Asymmetric induction of metal clusters by ligation of chiral ligands is intriguing in terms of the mechanism of chirality transfer and the stability of the resulting chiral structure. Here we report the asymmetric induction of C-centered hexagold(I) CAuI6 clusters into an asymmetrically twisted structure through monodentate, chiral benzimidazolylidene-based N-heterocyclic carbene (NHC) ligands. X-ray diffraction analysis revealed that the NHC-ligated CAuI6 cluster was diastereoselectively twisted with directionally selective, bond length expansion, and contraction of the Au···Au contacts and that the original cluster with high symmetry was transformed into an optically pure, asymmetric CAuI6 cluster with C1 symmetry. Moreover, the circular dichroism spectroscopy and the time-dependent density functional theory calculation confirmed that the asymmetrically twisted CAuI6 structure was maintained even in solution. Such asymmetric induction of configurationally stable metal clusters would greatly expand the molecular design possibilities of asymmetric catalysts and chiroptical materials by utilizing library chiral NHC ligands.