An efficient and environmentally friendly one‐pot sequential synthesis of functionalized nordazepam and a benzimidazoquinazoline analogue is reported, utilizing cobalt as the metal catalyst. The reaction proceeds via either the α‐alkenylation or dehydrogenative sp3 C‐H functionalization pathway. This transformation includes mild reaction conditions, operational simplicity, and good functional group tolerance. Additionally, this method is suitable for the gram‐scale synthesis of functionalized nordazepam and benzimidazoquinazoline compounds. Furthermore, the synthetic utility, photophysical properties and real‐life application of the synthesized derivatives were explored.