A mild, efficient and regioselective method for para‐amination of activated arenes has been developed through a combination of iron and copper catalysis. A diverse range of products were obtained from an operationally simple one‐pot, two‐step procedure involving bromination of the aryl substrate with the powerful Lewis acid iron(III) triflimide, followed by a copper(I)‐catalysed N‐arylation reaction. This two‐step dehydrogenative process for the regioselective coupling of aromatic C−H bonds with non‐activated amines was applicable to anisole‐, phenol‐, aniline‐ and acetanilide‐type aryl compounds. Importantly, the arene substrates were used as the limiting reagent and required no protecting‐group manipulations during the transformation.