AbstractA 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.