Site-selective trifluoromethylation of silyl dienol ethers derived from α,β-unsaturated aldehydes, ketones, and amides was achieved for the first time in the remote γ position. This photoredox catalyzed process is quite general to compounds bearing many functionalities and is applicable to the late-stage functionalization of biorelevant molecules. The use of S-perfluoroalkyl sulfoximines as ·RF radical sources enables the generalization of the reaction to other perfluoroalkyl groups (RF = CF2H, C4F9). Importantly, an unprecedented enantioselective C(sp3)-H perfluoroalkylation process is disclosed.