TMU-16-NH2 metal-organic framework was modified with glyoxal ligand via post-synthetic process, and the new support was applied for the immobilization of uniform Cu nanoparticles (NPs). These Cu NPs on MOF support with 1.2mol% loading was used as highly efficient heterogeneous catalyst for the synthesis of propargyl amines via a three-component reaction of amines, aldehydes, and alkynes (A3-coupling) under N2 atmosphere and solvent-free condition. In addition, this catalyst using simple separation could be recycled and reused for five consecutive cycles without appreciable loss in performance. The structure of the Cu@TMU-16-NH2-Gl was mainly maintained after reaction and also catalytic activity and stability were still high. Our strategy also efforts to develop an appropriate, simple, cost-effective, and green approach for organic reaction.