A mild and operationally simple C(sp<sup>3</sup> )-H trifluoromethylation method was developed for unactivated alkanes by utilizing a bench-stable Cu<sup>III</sup> complex, bpyCu(CF<sub>3</sub> )<sub>3</sub> , as the initiator of the visible-light photoinduced reaction, the source of a trifluoromethyl radical as a hydrogen atom transfer reagent, and the source of a trifluoromethyl anion for functionalization. The reaction was initiated by the generation of reactive electrophilic carbon-centered CF<sub>3</sub> radical through photoinduced homolytic cleavage of bpyCu(CF<sub>3</sub> )<sub>3</sub> , followed by hydrogen abstraction from an unactivated C(sp<sup>3</sup> )-H bond. Comprehensive mechanistic investigations based on a combination of experimental and computational methods suggested that C-CF<sub>3</sub> bond formation was enabled by radical-polar crossover and ionic coupling between the resulting carbocation intermediate and the anionic CF<sub>3</sub> source. The methylene-selective reaction can be applied to the direct, late-stage trifluoromethylation of natural products and bioactive molecules.