In recent years, particularly with the bloom of visible light photocatalysis, the N-centered radicals have received remarkable attention from synthetic community because these powerful species offer great opportunities for the construction of C-N bonds with many complementary aspects of both ionic and transition-metal-based methods in terms of retrosynthetic bond-disconnection and reaction selectivity. So far, various nitrogen-radical precursors have been developed, and the formed radicals can be broadly divided into four classes on the basis of N-hybridization and substituents, including ambiphilic iminyl radicals, electrophilic amidyl radicals, nucleophilic aminyl radicals, and their protonated analogues, electrophilic aminium radicals. Despite having received continuous progress, to the best of our knowledge, all the reported nitrogen-radical precursors are designed for producing single N-centered radicals, so they are only developed for installing single or undifferentiated amino functionalities. To realize the more challenging unsymmetrical diamination, we reasoned whether we could design a bifunctional reagent, which is in principle amenable to the simultaneous generation of two N-centered radicals at an equal rate but with different reactivities. If successful, then the regioselective stepwise addition of two differentiated N-centered radicals across carbon-carbon double bonds may provide direct access to the unsymmetrical vicinal diamines.