In summary, we have developed a mild, modular, and practical photoredox/iron dual-catalytic system for the direct access of diverse medicinally valuable 1,2-aryl(alkenyl) heteroatomic compounds from readily available starting materials such as (hetero)arenes, alkenes, and heteroatomic compounds. This methodology offers a broad substrate scope and is applicable to late-stage functionalization of complex bioactive molecules in a highly selective fashion, making it a valuable tool in drug discovery and development. The scalability of this protocol and the successful rapid synthesis of a range of bioactive molecules further underscore its practicality and synthetic utility.