A novel 3-D cuprous chloride polymer [CuCl(μ5-L)]n (1, HL = 1-tetrazole-4-imidazole-benzene) has been hydrothermally synthesized and structurally characterized. 1 displays a 3-D network with a bimodal fsc-3,5-Cmce-2 topological type constructed by the linkages of rare [CuCl]+ cations and L- ligands. The photoluminescence properties and density functional theory calculations of 1 have also been studied.