The possibility to exploit photonic energy in organic synthetic endeavors has dramatically impacted the way chemists assemble molecules. In particular, photocatalysis has enabled a convenient entry to open-shell intermediates, spurring the development of efficient manifolds for the generation of C-, 2 N-3 and O-4 centered radicals, as well as halogen radicals, which can be subsequently used to forge new chemical bonds. In contrast, boron-based congeners have long remained in obscurity, 7 mainly due to the intrinsic difficulties associated with the handling of these highly electron-deficient and unstable intermediates. However, ligated boryl radicals (LBRs), i.e. boron-centered radicals where the boron atom is coordinated with a suitable Lewis base, are more stable and provide a suitable entry for use in radical chemistry (Figure ). In particular, N-heterocyclic carbene-based (NHC) boranes are emerging as a useful LBR class: NHC boranes are stable crystalline compounds and a diverse array of NHCs can be ligated to boranes allowing to fine-tune the LBR properties. Notably, these LBRs can be uniquely paired with photocatalysis to generate the targeted boron-centered radicals. Herein, a photocatalyst absorbs visible light and engages with the ligated borane in a single-electron transfer step, which, upon deprotonation, generates the corresponding boryl radical. Although these boron-centered radicals have attracted mainly interest from the synthetic community as nucleophilic radicals, they have also been used in the role of halogen-atom transfer (XAT) agents. In the latter scenario, the halogen-affinity of the LBR is exploited for the homolytic activation of a C-X bond to yield carbon-centered radicals. However, this manifold has been so far only used to reduce C-X bonds into the corresponding C-H bond via a radical chain mechanism. Surprisingly, boryl radicals have been largely overlooked for the construction of C-C bonds (Figure ).