An iron‐catalyzed coupling reaction of O‐acyloximes and O‐benzoyl amidoximes with silyl enol ethers is reported. The protocol provides access to functionalized pyrroles, 1,6‐ketonitriles, pyrrolines and imidazolines via carbon‐centered radicals generated from an initially formed iminyl radical. The intramolecular cyclization and ring‐opening processes of the iminyl radical take place preferentially over reactions that proceed through a 1,3‐hydrogen transfer, providing insights into iron‐catalyzed reactions with oxime derivatives. The cheap and environmentally friendly iron catalyst, the broad substrate scope and the functional group compatibility make this protocol useful for synthesis of valuable nitrogen‐containing products. Functionalized heterocycles and ketonitriles were synthesized by coupling O‐acyloximes and O‐benzoyl amidoximes with silyl enol ethers using an iron catalyst. The three reaction pathways of the iminyl radical to carbon‐centered radicals gave rise to the diversity of products (see scheme).