AbstractHerein, synthesis of benzothiazoles via decarboxylative cross‐coupling between α‐keto acids and 2‐aminothiophenols under blue LED irradiation without using any photocatalyst or metal at room temperature is described. The formation of benzothiazole is driven by the EDA (electron donor‐acceptor) complex formed between α‐keto acid and 2‐aminothiophenol. This methodology gives easy access to 2‐substituted and ‐unsubstituted benzothiazoles in moderate to good yields. α‐Keto acids and 2‐aminothiophenols bearing different functional groups were easily transformed under the given conditions.magnified image