Functionalization of metal–organic framework (MOF) with various organic molecules to reinforce its surface potential in adsorption and stabilization of transition metal nanoparticles (NPs) is of great attention in creating/supporting ions metal within their framework and converting them into efficient heterogeneous catalysts. Here, we used a hybrid of inorganic–organic MOF (TMU-16-NH2) as an unparalleled compound for designing an efficient catalyst with nanoarchitecture via covalent functionalization of urea and 1,3-propane sultone ligands. This hybrid nanoporous MOF was further engaged as a support in the synthesis and stabilization of Cu NPs on its surface, and then, the obtained Cu-supported MOF was applied as a heterogeneous catalyst in the synthesis of propargyl amines derivatives under green reaction conditions with efficient recyclability.