We report the synthesis and characterization of a 3D Cu(II) coordination polymer, [Cu₃ (L¹)₂ (H₂ O)₈ ]·8H₂ O (1), with the use of a glycine-based tripodal pseudopeptidic ligand (H₃ L¹ = N,N^′,N^′′ -tris(carboxymethyl)-1,3,5-benzenetricarboxamide or trimesoyl-tris-glycine). This compound presents the first example of a 12-fold interpenetrated ThSi₂ (ths) net. We attempt to justify the unique topology of 1 through a systematic comparison of the synthetic parameters in all reported structures with H₃ L¹ and similar tripodal pseudopeptidic ligands. We additionally explore the catalytic potential of 1 in the A³ coupling reaction for the synthesis of propargylamines. The compound acts as a very good heterogeneous catalyst with yields up to 99% and loadings as low as 3 mol %.