Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) and halides are reported. The reduction of well-defined NHC–Au–Cl complexes produces clusters comprised of an icosahedral Au₁₃ core surrounded by a symmetrical arrangement of nine NHCs and three chlorides. X-ray crystallography shows that the clusters are characterized by multiple CH−π and π–π interactions, which rigidify the ligand and likely contribute to the exceptionally high photoluminescent quantum yields observed, up to 16.0%, which is significantly greater than that of the most luminescent ligand-protected Au₁₃ superatom cluster. Density functional theory analysis suggests that clusters are 8-electron superatoms with a wide HOMO–LUMO energy gap of 2 eV. Consistent with this, the clusters have high stability relative to phosphine stabilized clusters.