Abstract: | We report a powerful strategy for activation of C−H bonds to produce polysulfonamides by an atom‐economical and green method using iridium‐catalyzed direct C−H amidation polymerization (DCAP). After screening various directing groups, additives, silver salts, concentrations, and temperatures to optimize DCAP, high‐molecular‐weight (up to 149 kDa) and defect‐free polysulfonamides were synthesized from various bis‐sulfonyl azides. Although these polymers do not have conventional fluorescent conjugated cores, they emit blue light with large Stokes shifts and high quantum yields upon photoexcitation owing to an excited‐state intramolecular proton‐transfer process. |