In an early example, the radical silyldifluoromethylation of electron-deficient alkenes was reported. Herein, a very specific interaction, based on halogen bonding between the substrate and an NHC borane, was needed to trigger the desired C-X bond photolysis and subsequently initiate the radical chain mechanism sustained by the LBR (Figure ). Inspired by this report, we questioned whether it would be possible to realize a more general strategy to generate the pivotal ligated boryl radical. Such a pathway might allow the engagement of a broader array of substrates, ultimately leading to a general approach for C-C bond formation. Moreover, succeeding in this challenge would provide a cheap, tunable and sustainable alternative for other XATbased approaches using silyl 18 and -aminoalkyl radicals. To this end, we disclose our results regarding the development of a mild and broadly applicable protocol for C(sp 3 )-C(sp 3 ) bond formation using photoinduced XAT by NHC-ligated boryl radicals under both near-UV or blue-light irradiation (Figure ). The key role of the NHC-ligated boryl radicals in the operative reaction mechanism has been uncovered through a combination of experimental, spectroscopic and computational studies.