Mono- and binuclear structure of ternary complexes of Cu(Ⅱ):［Cu(H2biim)(Hssal) (H2O)2］·H2O(1) and {［Cu(MeHbiim)(Hssal)(H2O)］·0.5H2O}2 (2) (H3ssal=5-sulfonylsalicylic acid, H2biim=2,2′-diimidazole, MeHbiim=N-methyl-2,2′-diimidazole) were synthesized using 5-sulfosalicylic acid and imidazole derivatives as the ligands. The structures were characterized by elemental analysis, IR, UV-Vis, single crystal X-ray diffraction and TG analysis. X-ray crystallographic studies show that complex 1 belongs to monoclinic， P21/C space group. Each Cu (Ⅱ) ion is coordinated with one 5-sulfosalicylic acid anion, two water molecules and one biimidazole molecule to form five-coordinated mononuclear structural unit of distorted square pyramidal configuration. Binuclear Cu(II) complex 2 exhibits orthorhombic, P2(1)2(1)2(1) space group. One Cu(II) ion of binuclear structural unit is five-coordinated with geometry of square pyramid same as complex 1 and another Cu(II) ion is four-coordinated with geometry of quadrilateral plane. Compared to complex 1, 5-sulfonyl salicylic acid anion acted as a μ2 bis-monodentate bridging ligand in complex 2. The fluorescence spectrum analysis shows that the complex 2 has good fluorescence property.