A novel supramolecular complex {[Cu(II)(en) 2·H 2O]· [Cu(I) 2(CN) 4]} n (en=ethylenediamine), in which the cyanide-bridged Cu(I) forms the honeycomb-like skeleton host and the Cu(II) complex ion [Cu(en) 2·H 2O] 2+ is encapsulated in the center of the channel cavity of the skeleton, was synthesized by two different methods. The complex was also characterized by elemental analysis, ICP analysis, IR spectra and thermal analysis. The adsorption and desorption studies of the complex indicate that H 2O and NH 3 can be desorbed and re-adsorbed without collapse of the channel structure of the supramolecule. A novel supramolecular complex {[Cu (II) (en) 2 · H 2O] · [Cu (I) 2 (CN) 4]} n (en = ethylenediamine), in which the cyanide-bridged Cu The honeycomb-like skeleton host and the Cu (II) complex ion [Cu (en) 2 · H 2O] 2+ is encapsulated in the center of the channel cavity of the skeleton, was synthesized by two different methods. by elemental analysis, ICP analysis, IR spectra and thermal analysis. The adsorption and desorption studies of the complex indicate that H 2O and NH 3 can be desorbed and re-adsorbed without collapse of the channel structure of the supramolecule.