Herein we describe the direct, visible light-enabled activation of α-halo boronic esters to readily generate αboryl radicals in the presence of 2,6-disubstituted pyridines (Figure ). Intermolecular quench by styrenes enables expedient access to synthetically versatile E-allylic boronic esters after in situ elimination. Studies to determine the origin of activation revealed a substrate dependent mechanistic dichotomy, suggesting both EDA, and direct excitation enabled homolytic cleavage is operational. Capitalising on the mild reaction conditions, the introduction of a sensitiser enabled efficient stereodivergent access to the analogous Z-isomer, via selective energy transfer, further expanding accessibility of chemical space. Cognizant of the electron-deficient nature of the α-boryl radical, reaction optimization was explored using αiodo BPin (2a) in the presence of styrene ( ) as an electron-rich SOMOphile (Table ). In the absence of additives using UV-light no conversion to product was observed (Entry 1), however detection of iodine was noted indicating homolytic cleavage (see SI for full details). Judicious choice of 2,6-lutidine as an additive enabled the formation of product (E-1) with appreciable yield and selectivity at both 370 nm and 390 nm (Entry 2 and 3). Intriguingly, longer wavelengths enhanced stereoselectivity but led to unsatisfactory conversion to product (Entry 4). This subtle nuance could be easily rectified by an increase in photon flux to afford the product in good yield and excellent selectivity (Entry 5). While translation to longer wavelengths improved selectivity, conversion to product in the given timeframe was insufficient (Entry 6). We were interested to find that the reaction was highly specific to the use of 2,6-disubstituted pyridine additives with little to no reactivity observed with a range of other additives (Entry 7, see SI for full additive screen). Translation of model reaction conditions to α-iodo BPin (2b) was inefficient, presumably due to a loss in steric hinderence at the α-halo precursor leading to undesired reactivity (Entry 8). Modulating steric properties of the additive restored reactivity and selectivity (Entry 9), while control reactions demonstrated that both additive and light were required for the target transformation (Entries 10 and 11).