Here we report the preparation, structure, and spectroscopic properties of an intriguing copper(I) cyclophane-like dimeric complex [Cu2(dppa)2(bpy)2][BF4]2(2)¡B[Cu2(dppa)2(mbpy)2][BF4]2(3)¡B[Cu2(dpbp)2(bpy)2][BF4]2(7)©M[Cu2(dppb)2(bpy)2] [BF4]2(8), containing phenyl phosphine bridge ligands, such as diphenylphosphino acetylene (dppa), 1,4-bis(diphenylphosphino)benzene (dppb) and 4,4'-bis(diphenyl phosphino)biphenyl (dpbp). As a building unit, the complex [Cu2(dpbp)2(NCMe)4] [BF4]2(9) containing labile acetonitrile molecules those can be easily substituted by anionic ligands, is expected to combine with suitable linkers to synthesize supramolecular arrays with shapes of polygons and polyhedra.