This work describes BiCl3’s catalytic activity in synthesizing N‐arylbenzimidazole and the phosphorylation of substituted coumarins with alkyl and aryl phosphites. This framework is utilized to synthesize a variety of 2‐aminobenzimidazole and coumarin derivatives in moderate to high yields under mild reaction conditions. The catalyst employed is highly productive, less hazardous, and inexpensive, making it desirable economically and environmentally.