Binuclear complex ［Cu2(μ-I)2(phen)2］·CH3CN(1)(phen=1,10-phenanthroline) was synthesized under solvothermal conditions and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. X-ray diffraction analysis reveals that complex 1 is monoclinic, space group P21/n, and the cell parameters are: a=10.505 , b=23.628 , c=10.676 , α=90°, β=91.40° and γ=90°. the authors have studied the luminescence property of 1, Complex 1 has blue-purple luminescence in solutions of DMSO with emission bands at 369, 380 and 460sh nm; and has red luminescence in the solid state at room temperature with a broad emission band at 650～678 nm. These all can be attributed to the π*→π transition based on the ligand. In the solid state, the emission frequencies for complex 1 are red-shifted about 280 nm compared with their emission maximum peaks in solutions of DMSO. This red-shift of emission energy from solution to solid is likely to be caused by the intermolecular π—π packing interaction in the solid state which effectively decreases the energy gap. The fluorescence decay curve of complex 1 indicated that the processes of decay consists of two components, whose corresponding lifetimes are τ1=1.36 μs and τ2=5.98 μs, corresponding factors are 50.21% and 49.79% in DMSO solutions, and τ1=1.42 μs, τ2=8.85 μs, corresponding factors are 51.15% and 48.85% in the solid state.