Herein, we report a mild, operationally simple method for synthesis of α,α‐difluoroketones through selective single defluorination of trifluoroketones and subsequent difluoroalkylation of C(sp3)–H bonds at room temperature within a single step. By successfully difluoroalkylating unfunctionalized ethers and benzyl radical precursors, we demonstrated the broad applicability of this method. The mechanistic study supports that the success of the reaction is probably attributed to the dual roles of trimethylsilyl chloride under the photocatalyzed conditions: 1) fluoride anion scavenger; and 2) chlorine radical source which promote hydrogen atom transfer (HAT) reaction.