A nickel-catalyzed site-selective intermolecular amidation of saturated C(sp³)−H bonds is reported. This mild protocol exhibits a predictable reactivity pattern to incorporate amide functions at C(sp³)−H sites adjacent to nitrogen and oxygen atoms in either cyclic or acyclic frameworks, thus offering a complementary reactivity profile to existing oxidative-type processes or metal-catalyzed C(sp³)−N bond-forming reactions operating via two-electron manifolds.