Two new copper coordination polymers [Cu(μ24,4'-bipyridine)(NO2)2]n (C10H8-(C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthesized by hydrothermal reaction and determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic, space group P2/m with a =4.7740(10), b = 11.039(2), c = 5.6752(14)(°A), β = 91.394(9)°, V = 299.00(11)(°A)3, Z = 1, Dc = 1.731g/cm3, F(000) = 157 and μ(MoKa) = 0.7107 mm-1. Compound 2 crystallizes in monoclinic, space group P2/n with a = 12.916(2), b = 11.149(1), c = 15.006(2)(°A),β =106.642(6)°, V= 2070.3(5) (°A)3,Z = 2, Dc = 1.510 g/cm3, F(000) = 970 and μ(MoKa) = 0.7107 mm-1. In the structure of compound 1, the metal atom is in a slightly distorted octahedral CuO4N2 geometry surrounded by four O atoms of two NO2 ligands in the equatorial positions and two N atoms from 4,4'-bipyridine ligands in the axial sites, and the 4,4'-bipyridine ligands bridge the neighboring Cu2+ atoms to form polymeric chains in the lattice. Compound 2 has a 2D square-grid network structure. The square grids are superposed on each other to form a channel framework. The square cavity has dimensions of 11.148(2)(°A) × 11.229(3)(°A). Every two guest 4,4'-bipyridine molecules are clathrated in each hydrophobic host cavity and further stabilized by π-π stacking and hydrogen bonding interactions.