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A novel Cu(Ⅱ) complex has been prepared by means of self-assembly of CuCl2, 1-hexylimidazole L and oxalic acid (H2OX) in the presence of triethylamine, and structurally characterized by X-ray diffraction analysis. In complex 1, 1-D polymer chains are formed through pentacoordinated Cu(Ⅱ), oxalate and bridging chlorine atoms. In the crystal packing of 1, the imidazole ring head-to-tailπ-πstacking interactions exist between 1-D polymer chains and extend the 1-D polymer chains into 2-D supramolecular layers. The fluorescence emission spectra of L and 1 were described.