Metal clusters bridge atoms and nanoparticles as ideal models for studying structure–property relationships. However, ligand-protected coinage metal clusters (Au/Ag/Cu) often suffer from poor stability and weak emission, hindering precise synthesis of chiral, highly luminescent clusters. We developed site-specific modification and directed assembly to enhance stability and luminescence. We also established shell chirality control for efficient synthesis of enantiopure clusters, revealing shell-regulated electronic mechanisms that push luminescence efficiency toward the theoretical limit. Furthermore, we elucidated hierarchical chiral assembly mechanisms enabling exceptional circularly polarized luminescence (CPL), positioning these clusters among top CPL-active materials.