B 10 H 10 ] 2 } (3) have been synthesized by the reactions of CuX (X = Cl, Br and I) with the closo ligand 1,2-(PPh 2 ) 2 -1,2-C 2 B 10 H 10 . All these complexes were characterized by elemental analysis, FT-IR, 1 H and 13 C NMR spectroscopy and X-ray structure determination. Single crystal X-ray structure determinations show that every complex contained di-µ-X-bridged structure involving a crossed parallelogram plane formed by two Cu atoms and two X atoms (X = Cl, Br, I). The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two P atoms of the PPh 2 groups connected to the two C atoms of carborane (Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. To the best of our knowledge, this is the first example of copper(I) complexes with 1,2-diphenylphosphino-1,2-dicarba-closo-dodecaborane as ligand characterized by X-ray diffraction. The catalytic property of the complex 3 for the amination of iodobenzene with aniline was also investigated.