Whilst conventional retrosynthetic logic has culminated in a plenum of C-B bond forming processes, disconnecting the adjacent σ-bond has been less-intensively investigated. Motivated by the emergent popularity of α-boryl radicals as promising open-shell alternatives, opportunities exist to complement existing borylation methods by radical-based paradigms to enable the rapid construction of saturated organoboron motifs (Figure ). Whereas early reports on the generation of α-boryl radicals leveraged radical initiators, this has been superseded by photochemical platforms to enable in situ generation via two distinct pathways; β-addition or α-activation. The former has gained much attention in recent years and relies on independent radical generation via direct excitation or photoredox activation, followed by addition to a vinyl or strained organoboron species. 9b Intriguingly, subsequent reactivity of the α-boryl radical is often governed by boron hybridisation. Addition to organometallic-derived boronates has been leveraged to generate elegant pairing with 1,2-metalate rearrangements, while addition to vinyl boronic esters, has also resulted in fruitful mergers with transition metal cascades. Light-enabled α-activation strategies, are however, comparatively under-explored but are attractive based on considerations of operational simplicity and atom economy. Studer and coworkers have demonstrated that H-atom abstraction of organometallic-derived organoborates enable the intramolecular transfer of carbon and boron units to the α-position. In addition, the activation of easily accessible α-iodides is currently achieved via photoredox, halogen atom transfer or unique examples via photoactivation in the presence of transition metal complexes. Since photoredox or transition-metal catalysts are prerequisites for photo-activation in these examples, strategies that would facilitate the reactivity to be emulated by direct irradiation using only visible light would be highly enabling.