Abstract The thermal decomposition of the benzenesulfenanilides (Ia)‐(Ic) in benzene, furan (IV) or benzene/cyclohexene (VI), and of the 2‐phenylbenzenesulfenanilides (Id)‐(If) in benzene at 85 or 150 °C is studied in detail (tables) and two distinct pathways relevant for the reactions are discussed.