Theoretical calculations reveal that the HOMOs and LUMOs of these chiral materials are primarily localized on the donors of carbazole, triphenylamine, and the acceptor of benzonitrile, respectively, but have partial overlap on the phenyl bridge (Supplementary Fig. ). The inadequate separation between HOMOs and LUMOs results in substantial theoretical energy gaps of 0.95 and 0.83 eV for (S)-PCNCP and (S)-PCNTPA between the lowest excited triplet (T1) and singlet (S1) states, suggesting that the reverse intersystem crossing (RISC) process from T1 to S1 states is unlikely to occur in these materials. However, there are small energy gaps (0.08-0.22 eV) between high-lying excited triplet (T2-T4) states and S1 state, whereas the energy gaps between T2 and T1 states are as large as 0.87 and 0.98 eV, respectively. Additionally, considerable spin-orbital coupling (SOC) matrix elements are found between T2-T4 and S1 states. For example, the SOC matrix elements between T2 and S1 states are 1.108 and 0.760 cm -1 for (S)-PCNCP and (S)-PCNTPA, respectively (Supplementary Fig. ). These simulation results suggest that the high-lying RISC (hRISC) process may occur in these chiral materials, which is conducive to increasing exciton utilization and improving EL efficiencies.