The triazine-based trisphosphine, 2,4,6-tris-(diphenylphosphino)-1,3,5-triazine (1) was prepared in improved yield by reacting cyanuric chloride with 3 equiv of trimethylsilyldiphenylphosphine. The solid-state structure of 1 showed short intermolecular P...P contacts of 3.362 angstrom, which is significantly shorter than the sum of the van der Waals radii of phosphorus atoms (3.6 angstrom). The reaction of 2,4,6-tris(diphenylphosphino)-1,3,5-triazine (1) with copper(I) salts in a 2:3 molar ratio yielded various cydophane-type complexes in quantitative yield. The solid-state structures of these clusters have been found to depend on the size of the halide ions, the solvent employed, and the reaction conditions. Copper(I) chloride formed a monomeric metallocydophane, whereas copper(I) bromide and copper(I) iodide derivatives preferred dimeric and 1D-polymeric structures, respectively. The tricationic complexes derived from Cu-I ion and 2,4,6-tris(diphenylphosphino)-1,3,5-triazine also adopted monomeric metallocydophane structures. These complexes have been employed in the A(3) coupling reaction under microwave irradiation. The copper(I) iodide derivative showed excellent catalytic efficiency.