AbstractAmmonia, NH₃, is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber–Bosch process, from the very stable dinitrogen molecule, N₂ and dihydrogen, H₂. This process requires high temperatures and pressures, thereby generating ca 1.6 % of the global CO₂ emissions. Alternative strategies are needed to realize the functionalization of N₂ to NH₃ under mild conditions. Here, we show that boron‐centered radicals provide a means of activating N₂ at room temperature and atmospheric pressure whilst allowing a radical process to occur, leading to the production of borylamines. Subsequent hydrolysis released NH₄⁺, the acidic form of NH₃. EPR spectroscopy supported the intermediacy of radicals in the process, corroborated by DFT calculations, which rationalized the mechanism of the N₂ functionalization by R₂B radicals.