In summary, we have established a general and mild protocol for the α-C-H cyanation of tertiary amines. Suitable substrates include tertiary aliphatic, benzylic, and anilinetype substrates as well as complex substrates. Functional groups tolerated under the reaction conditions include various 6-and 5-membered and bicyclic heterocycles, ketones, amides, olefins, and alkynes. This broad substrate scope is remarkable, as comparable reaction conditions for the α-C-H cyanation of tertiary amines frequently employ peroxide-based oxidants (e.g., t BuOOH). Such oxidants typically lead to free radicals as intermediates, which can attack olefinic, alkyne, and heterocyclic substructures of complex amine substrates and are thus fundamentally limited in their scope. The presented work circumvents this issue by designing an Fe-based catalyst system that potentially relies on substrate binding and a radical-rebound mechanism. This hypothesis supports that functional groups labile in the presence of radicals are readily tolerated. Importantly, all reaction components of the catalytic system are readily available, allowing implementation of the presented methodology without lengthy catalyst synthesis. Due to all these benefits, we consider the presented protocol to be the most general methodology for the α-C-H cyanation of tertiary amines to date.