Bright and efficient chiral coinage metal clusters show promise for use in emerging circularly polarized light-emitting materials and diodes. To date, highly efficient circularly polarized organic light-emitting diodes (CP-OLEDs) with enantiopure metal clusters have not been reported. Herein, through rational design of a multidentate chiral N-heterocyclic carbene (NHC) ligand and a modular building strategy, we synthesize a series of enantiopure Au(I)-Cu(I) clusters with exceptional stability. Modulation of the ligands stabilize the chiral excited states of clusters to allow thermally activated delayed fluorescence, resulting in the highest orange-red photoluminescence quantum yields over 93.0% in the solid state, which is accompanied by circularly polarized luminescence. Based on the solution process, a prototypical orange-red CP-OLED with a considerably high external quantum efficiency of 20.8% is prepared. These results demonstrate the extensive designability of chiral NHC ligands to stabilize polymetallic clusters for high performance in chiroptical applications.