A pair of multi-emission enantiomers, (R)-DO-PSeZ and (S)-DO-PSeZ, was designed and synthesized by integrating Se-induced conformationally isomeric donors with a chiral carbonyl-containing acceptor into a unified molecular framework. The enantiomers showed white emission with blue, yellow and red multi-emission bands in solution and film at CIE coordinates of (0.39, 0.35) and (0.33, 0.34), respectively. Doped film of the enantiomers achieved a high photoluminescence quantum yield of 42%, accompanied by mirror-image white circularly polarized photoluminescence (WCPPL) signals with a |g𝑃𝐿| value of 2.6 × 10-3. Moreover, the enantiomers also showed white circularly polarized electroluminescence (WCPEL) in organic light-emitting diodes with CIE coordinates of (0.29, 0.33) and EQEmax of 3.1%. Notably, this work represents the first single-molecule multi-emission WCPL materials and achieved the highest performance for white OLEDs based on single-molecule organic materials with phosphorescent properties. Furthermore, leveraging Bragg reflection from dual-layer cholesteric liquid crystals, the enantiomers achieved |gPL| and |gEL| values of 1.85 and 1.88, respectively, marking the highest reported values for WCPPL and WCPEL to date.