Abstract An efficient I 2 ‐promoted Povarov multicomponent reaction for the synthesis of 2,2′‐biquinolines or N ‐heteroaromatic benzothiazole using 2‐methylquinoline or 2‐methylbenzo[ d ]thiazole, arylamines, and α ‐ketoesters was developed. The methyl group of methyl aza‐arenes incorporated in the Povarov reaction via an iodination/Kornblum oxidation sequence. This method was achieved through a one‐pot two‐step process without the need for transition metals, demonstrating excellent scalability in synthesis.