In the past decade, organic-inorganic hybrid materials have intrigued great interest for their various architectures and potential application in catalysis, gas storage, non-linear optics, ionexchange, luminescence, magnetism and many other fields [1-2].As our ongoing research project dealing with the organic-inorganic hybrid solids based on α,ω-bis(benzotriazole)alkane ligands,1,6-bi(benzotriazole)hexane (BBTH) with much longer alkane spacer is selected since we did not find any compounds constructed from this ligand to date.In the present study, the solvothermal reaction of the BBTH with CuCl generated a novel three-dimensional hybrid solid, namely,{[CuCl]2(BBTH)}n (1), which were characterized via X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction (XRPD), FT-IR, TGA and photoluminescence measurements.