A new complex [Rh(COD)(2,2'-bipy)]center dot[Rh(COD)Cl-2] (COD = 1,5-cyclooctadiene, 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P (1) over bar with a = 7.4782(14), b = 10.1400(11), c = 16.6982(14) angstrom, a = 103.494(11), beta = 91.996(13), gamma = 103.829(12)degrees, C26H32Cl2N2Rh2, M-r = 649.26, V = 1190.0(3) angstrom(3), D-c = 1.812 g/cm(3), Z= 2, F(000) = 652, mu(MoK alpha) = 1.629 mm(-1), R = 0.0286 and wR = 0.0463 for 3718 observed reflections (I > 2 sigma(I)). The complex was linked to form 1D chains by hydrogen bonding interaction (C-H center dot center dot center dot Cl), and further to construct a 2D layer structure by pi center dot center dot center dot pi stacking interactions between the pyridine rings of 2,2'-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.