Abstract Herein, we report a cross‐coupling reaction between aryl sulfonyl chlorides and arylthianthrenium salts, catalyzed by palladium without ligand. This process involves the desulfonylative of aryl sulfonyl chlorides and pre‐ thianthrenation activation steps of aromatic hydrocarbons, leading to the selective formation of the biaryl compounds. The method demonstrates compatibility with various functional groups. Furthermore, the late‐stage functionalize‐tion of bioactive compounds underscores the favorable implications of this approach in the innovation of novel pharmaceutical agents.