Two new CuI-phenanthrene-9-carbonitrile (phencn) based coordination polymers formulated with [CuI(phencn)] n (1) and [Cu 2 I 2 (phencn)] n (2) are easily accessible by the reaction of copper(I) iodide with phencn in different stoichiometric ratios of the reactants. 1 contains Cu 2 I 2 double-stranded stair that can be regarded as two CuI zigzag single chains connected together via Cu―I bonds, while 2 consists of novel one-dimensional Cu 6 I 6 hexagonal cage chain that can be conveniently described as two Cu 2 I 2 double-stranded stairs connected together via Cu―I bonds. The monodentate phencn ligands regularly stack along both sides of the (CuI) n skeletons in 1 and 2. IR, elemental analysis and XRPD confirmed the phase purity of the bulk materials. The photoluminescent properties of 1 and 2 in the solid state at ambient temperature are also investigated.