Hydrothermal reactions of CuCN, K3[Fe(CN)6] with 2,2′-bipyridine, 1,10-phenanthroline or 2,6-bis(1,2,4-triazolyl)pyridine (btp) afford three coordination polymers, [Cu7(CN)7(bipy)2] n (1), [Cu2(CN)2(phen)] n (2) and [Cu3(CN)3(btp)] n (3). Complex 1 displays 1D polymeric ribbons which are assembled through Cu ··· Cu and π–π stacking interactions into a 3D framework. Complex 2 shows a 1D zigzag chain structure in which phen is a side ligand. In 3, the copper cyanide 2D polymeric networks are connected by tridentate btp to form a 3D metal-organic framework. These coordination polymers exhibit strong fluorescent emissions in the solid state.