Low-valent organonickel radical complexes are common intermediates in cross-coupling reactions and metalloenzyme-mediated processes. The electronic structures of N-ligand supported nickel complexes appear to vary depending on the actor ligands and the coordination number. The reduction products of a series of divalent (pyrox)Ni complexes establish the redox activity of pyrox in stabilizing electron-rich Ni­(II)–alkyl and −aryl complexes by adopting a ligand-centered radical configuration. The reduced pyrox imparts an enhanced trans-influence. In contrast, such redox activity was not observed in a (pyrox)­Ni­(I)–bromide species. The excellent capability of pyrox in stabilizing electron-rich Ni species resonates with its proclivity in promoting the reductive activation of C­(sp3) electrophiles in cross-coupling reactions.