A highly selective and general photocatalytic C–F borylation protocol that employs a rhodium biphenyl complex as a triplet sensitizer and the nickel catalyst [Ni(IMes)₂] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the C–F bond activation and defluoroborylation process is reported. This tandem catalyst system operates with visible (blue, 400 nm) light and achieves borylation of a wide range of fluoroarenes with B₂pin₂ at room temperature in excellent yields and with high selectivity. Direct irradiation of the intermediary C–F bond oxidative addition product trans-[NiF(Ar^F)(IMes)₂] leads to very fast decomposition when B₂pin₂ is present. This destructive pathway can be bypassed by indirect excitation of the triplet states of the nickel(II) complex via the photoexcited rhodium biphenyl complex. Mechanistic studies suggest that the exceptionally long-lived triplet excited state of the Rh biphenyl complex used as the photosensitizer allows for efficient triplet energy transfer to trans-[NiF(Ar^F)(IMes)₂], which leads to dissociation of one of the NHC ligands. This contrasts with the majority of current photocatalytic transformations, which employ transition metals as excited state single electron transfer agents. We have previously reported that C(arene)–F bond activation with [Ni(IMes)₂] is facile at room temperature, but that the transmetalation step with B₂pin₂ is associated with a high energy barrier. Thus, this triplet energy transfer ultimately leads to a greatly enhanced rate constant for the transmetalation step and thus for the whole borylation process. While addition of a fluoride source such as CsF enhances the yield, it is not absolutely required. We attribute this yield-enhancing effect to (i) formation of an anionic adduct of B₂pin₂, i.e., FB₂pin₂^–, as an efficient, much more nucleophilic {Bpin^–} transfer reagent for the borylation/transmetalation process, and/or (ii) trapping of the Lewis acidic side product FBpin by formation of [F₂Bpin]⁻ to avoid the formation of a significant amount of NHC-FBpin and consequently decomposition of {Ni(NHC)₂} species in the reaction mixture.