A general and highly regioselective synthetic protocol for structurally diverse N-heteroaryl-fused phenanthridines has been developed. Varieties of fluorescence molecules comprising imidazole-fused, benzoimidazole-fused, indole-fused and pyrrole-fused phenanthridines were obtained by this modular approach, some of which exhibit excellent blue-emitting performance, high quantum yields, long fluorescence lifetimes, interesting electrochemical properties, and thermal stabilities.