Abstract: Utilizing 1, 2-bis (diphenylphosphino) ethane (dppe), 1, 4 -bis (diphenylphosphino) butane (dppb), and cuprous halide as the starting materials, a trinuclear copper (Ⅰ) bromide complex Cu₂ (μ-dppe)(μ-Br)₂(μ-dppe)₂CuBr (1) and a binuclear copper (Ⅰ) iodide complex Cu (dppb)Ⅰ₂(μ -dppb) (2) were synthesized and structurally characterized. As revealed by single-crystal X-ray diffraction, compound 1 is a trinuclear copper (Ⅰ) complex in which the Cu1 and Cu2 atoms adopt a common four -coordinate mode. Each connects with two bromide and two phosphorus atoms, respectively, forming a distorted tetrahedral configuration. The Cu3 atom is trigonally coordinated via two phosphorus and one bromide atoms by generating a plane triangle. These three copper (Ⅰ) atoms (Cu1, Cu2, Cu3) give a nearly isosceles triangle together. Compound 2 is a binuclear Cu (Ⅰ) complex, in which these three dppb ligands offer two kinds of coordination fashions: two of them are chelating, one for each copper atom. However, the third one acts as a bridge assembling two same Cu (dppb)Ⅰ moieties into a copper (Ⅰ) dimer.