Abstract: Solvothermal reaction of the flexible ligand 1,6-bi(benzotriazole)hexane (BBTH) with CuCl generated a 3-D hybrid solid, {[CuCl]₂(BBTH)}_n (1), which was investigated by elemental analysis, FT-IR, X-ray powder diffraction (XRPD), X-ray single-crystal diffraction, TG/DTA, and photoluminescence measurements. Compound 1 crystallizes in the tetragonal system, space group I4(1)/a, a = b = 17.636(2) Å, c = 13.5345(15) Å, V = 4209.6(9) ų, Z = 8. The distorted tetrahedral geometry of Cu(I) is defined by two chlorides and two N donors from different BBTH ligands. Adjacent copper atoms are connected by μ₂-Cl to give a 1-D zigzag inorganic chain, and further linked by BBTH ligands via μ₄-bridging, forming the 3-D hybrid structure of 1. Cu(I) atoms and BBTH ligands can be regarded as two kinds of non-equivalent 4-connected nodes, which lead to an unusual topological network with Schläfli symbol of (3².8.9².10)₂(3².8².9²). Compound 1 exhibits high thermal stability and shows strong red fluorescence emission at 538 nm in the solid state at ambient temperature.