Divalent propargylamines are a pre‐eminent class of intermediates to multidentate ligands which have wide implications for use in catalysis. Here, a highly chemoselective and versatile protocol for the construction of novel cyclic divalent propargylamines has been accomplished under microwave irradiation. This sequential transformation comprises a copper‐catalyzed annulation/ A3‐coupling/A3‐coupling of a primary diamine with formaldehyde solution, and two alkynes, directly providing a diverse set of N,N'‐dipropargyl imidazolidines and hexahydropyrimidines in the moderate to excellent yields.