This paper describes two copper(I) supramolecules with the same anion and cation but quite different topologies and properties. The reaction of [Cu(CH(3)CN)(4)]PF(6) and 1,2,4,5-tetracyanobenzene (TCNB) leads to two novel polymeric coordination compounds, [Cu(2)(TCNB)(3)](PF(6))(2)(Me(2)CO)(4)( )()(1) and [Cu(2)(TCNB)(3)](PF(6))(2) (2), depending on the solvents used. The crystal structures have been determined by single-crystal X-ray diffraction. Crystal data are as follows. 1: C(21)H(15)N(6)O(2)CuPF(6), monoclinic, P2(1)/a, a = 11.553(4) Å, b = 16.135(7) Å, c = 15.046(3) Å, beta = 108.08(2) degrees, Z = 4. 2: C(15)H(3)N(6)CuPF(6), orthorhombic, Cmcm, a = 28.282(3) Å, b = 10.337(3) Å, c = 16.285(4) Å, Z = 16. In both polymers, copper(I) ions have similar pseudotetrahedral environments and the four coordination sites are fully occupied by the four bridging ligands, two &mgr;(2)-TCNB and two &mgr;(4)-TCNB groups. Polymer 1, obtained in acetone, revealed a two-dimensional zigzag sheet network between copper(I) ions, whereas 2, synthesized in methylethyl ketone, displayed a three-dimensional porous framework with different functional groups (or atom) in different cavities. The redox, magnetic, and conductive behaviors of both complexes are discussed. It is demonstrated that the two complexes give different physicochemical properties.