The following protocol can be applied in the selective cross-coupling reaction of an amine with an aryl iodide or bromide using a copper (Cu)-based catalyst to provide the corresponding N-aryl amine. The general procedure described in this text includes a detailed description of an appropriate reaction setup, two methods for assaying the crude reaction mixture (gas chromatography and thin layer chromatography) and a procedure for the isolation, purification and characterization of the anticipated product. Manipulation of the reagents can be done in the air, without the use of a glovebox; however, the cross-coupling reactions must be performed in a sealed reactor under an inert atmosphere. Three C–N bond-forming reactions are included in the protocol as representative examples of this procedure. Although the reactions can proceed in <1 h, the protocols, including workup, generally take 6–30 h to complete.