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Abstract Multifunctional organoboron compounds increasingly enable the simple generation of complex, Csp³‐rich small molecules. The ability of boron‐containing functional groups to modify the reactivity of α‐radicals has also enabled a myriad of chemical reactions. Boronic esters with vacant p‐orbitals have a significant stabilizing effect on α‐radicals due to delocalization of spin density into the empty orbital. The effect of coordinatively saturated derivatives, such as N‐methyliminodiacetic acid (MIDA) boronates and counterparts, remains less clear. Herein, we demonstrate that coordinatively saturated MIDA and TIDA boronates stabilize secondary alkyl α‐radicals via σ_B‐Nhyperconjugation in a manner that allows site‐selective C−H bromination. DFT calculated radical stabilization energies and spin density maps as well as LED NMR kinetic analysis of photochemical bromination rates of different boronic esters further these findings. This work clarifies that the α‐radical stabilizing effect of boronic esters does not only proceed via delocalization of radical character into vacant boron p‐orbitals, but that hyperconjugation of tetrahedral boron‐containing functional groups and their ligand electron delocalizing ability also play a critical role. These findings establish boron ligands as a useful dial for tuning reactivity at the α‐carbon.