The first direct C(sp3)−H bond sulfonylation and sulfuration reactions of isoquinoline‐1,3‐(2H,4H)‐diones have been developed under transition‐metal‐free conditions. Using air as the sole oxidant, the C‐4 sulfonylated products of isoquinolones were synthesized using sulfinates as the sulfonating agents and NaI as an iodine source in AcOH/DMSO. The sulfuration reaction was realized for the first time using disulfides as sulfurating partners in a t‐BuOK/DMF catalytic system. Both procedures undergo a free radical reaction process with the advantages of high atom economy, green reaction conditions, readily accessible materials and broad substrate scope.

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