Abstract A mild and safe photochemical methodology has been developed to access difluoroamidosulfonylated dioxodibenzothiazepines via three‐component radical bicyclization cascades. This photocatalyst‐free transformation avoids cumbersome photocatalyst removal procedure and potential toxicity. Mechanistic experiments reveal the generation of an electron donor‐acceptor (EDA) complex in the reaction process. Moreover, synthetic value of the protocol is further demonstrated by gram‐scale reaction, conversion of product and total synthesis of antidepressant drug. magnified image