Very recently, bismuth redox catalysis has been established as an emerging platform for organic synthesis. In this context, our group has shown how polar Bi(III/V) or Bi(I/III) catalytic cycles can lead to the development of C-F, C-O, or C-H bond-forming reactions, among others. Nevertheless, even though persistent and stable radicals of heavier main-group elements are known, the studies for bismuth are much more limited, and bismuth radical catalysis has been significantly underexplored. Bi(II/III) catalytic cycles have been postulated for the living radical polymerization of alkenes, or the cycloisomerization of 4iodoalkenes. This, together with further reports probing the existence of bismuth(II)-centered radicals, prompted us to explore the behavior of the Bi(I/II) pair in SET-based oxidative additions of redox-active alkyl electrophiles. Here, we disclose how a well-defined bismuthinidene (1) reacts with alkyl phthalimide esters and alkyl Katritzky salts to give alkyl-bismuth(III) adducts, which were found to behave as Bi-C radical-equilibrium complexes (Fig. , bottom). Additionally, we discovered that α-amino alkyl-radical fragments resulting from this process can be easily oxidized by Bi(II), giving rise to iminium ions that can be trapped by N-nucleophiles. This observation led to the development of a Bi-catalyzed radical C-N cross-coupling reaction with a wide scope of both coupling partners (Fig. , top). In spite of the vast number of alkyl-radical couplings developed during the past decade, seldom examples of C(sp 3 )-N bond formation from redox-active radical precursors have been reported, mainly relying on photoredox setups, electrochemical synthesis, or the use of an excess of chemical oxidant. In this report, we demonstrate that catalytic amounts of a Bi(I) complex can promote this type of transformation in an autonomous manner, without the need of a photoredox system, a chemical oxidant, an external base, or an electrochemical setup.