Excited-state palladium catalysis is an efficient process for the alkylation of diverse organic compounds via the generation of alkyl radicals from alkyl bromides and iodides. However, the generation of alkyl radicals from more stable alkyl chlorides remains challenging. Herein, we demonstrate the excited-state palladium-catalyzed synthesis of oxindoles and isoquinolinediones via alkylation/annulation reaction by overcoming inherent limitations associated with unactivated C(sp3)-Cl bond activation at room temperature.