Solvothermal reactions of copper(l) cyanide with tetramethylammonium salts in anhydrous tetrahydrofuran (THF) lead to two novel halogeno(cyano)cup rates, namely, [Me4N][Cu-3(CN)(2)Br-2] (1) with a 1-D ribbon motif and [Me4N](2)[Cu-4(CN)(5)Cl] (2) with a 3-D nanoporous framework. In 1, four Cu(I) ions are connected via two mu-Br and two mu 3-Br atoms into a neutral [Cu4Br4] cluster, and such clusters are further double bridged by [Cu(CN)(2)](2-) linkers to form a 1-D ribbonlike chain. While in 2, Cu(I) ions are connected via mu-CN and mu(3)-CN ligands and gamma-Cl atoms into a 2-D fluctuant sheet along the a-c plane, and these sheets are further linked by another kind of mu-CN ligand to form a 3-D nanoporous framework in whose channels reside [Me4N](+) cations. Results of optical and luminescent studies indicate that both two complexes are potential materials for semiconductors and long-lived highly luminescent materials.