A new copper(I) iodide coordination polymer, [(CuI)3(dtb)]n (1) (dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene) has been synthesized solvothermally and structurally characterized by single crystal and powder X-ray diffractions, elemental analysis, IR, and thermogravimetric analysis. Overall, 1 exhibits a 2D hybrid structure containing dtb as structure-directing agents (SDAs) and 1D Cu3I3 chain as inorganic moiety. The copper-iodide chain can be regarded as two Cu2I2 rhomboids are connected by CuI fragments via Cu–I bonds. Dtb act as bridging ligands regularly link the Cu3I3 chains along both sides through Cu–N bonds to give the final 2D network. Moreover, solid state luminescent property of 1 has been investigated at room temperature. [ABSTRACT FROM AUTHOR]