In conclusion, we have developed a catalytic enantioselective synthesis to obtain CBBC 2a from DBC 1a via internally hydroxy-substituted DBC derivative 3a. This oxidative inner-bond-cleavage strategy is applicable to peripherally functionalized DBC derivatives and PAHs. This new synthetic strategy has enabled detailed systematic investigations into the chemistry of CBBC, including an exploration of its fundamental physical properties and functionalization. This exploration revealed that CBBC is configurationally stable even at high temperature and emits efficient CPL with high g values. The peripheral functionalization of CBBC with carbazole afforded D-A-type emitter 9, which shows TADF activity and emits CPL with a high g value of 1.0 × 10 -2 .