A novel copper(Ⅱ) coordination polymer of {[Cu3L2(4,4?-bipy)4](Cl O4)2·20H2O}n(1) was synthesized by the reaction of H2L(C6H5N(CH2COOH)2, phenyliminodiacetic acid), Cu SO4·5H2O, Na Cl O4·H2O and 4,4?-bipy(4,4?-bipyridine) in water/methanol, followed by slow evaporating at room temperature. The compound was characterized by elemental analysis(EA), infrared spectroscopy(IR), thermogravimetric analysis(TGA) and single-crystal/powder X-ray diffraction. The result of single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic crystal system with C2/c space group, a = 2.9974(4), b = 1.7270(2), c = 2.0007(3) nm, β = 128.793(2)o, V = 8.0722(19) nm3, Z = 4, Dc = 1.472 g·cm-3, μ = 0.942 mm-1, F(000) = 3716, R = 0.0487 and w R = 0.1204(I > 2σ(I)). The basic structural unit of 1 is a trinuclear cluster unit of [Cu3L2]2+, which is constructed by two μ2-L2- ligands bridging and chelating three Cu(Ⅱ) ions. These [Cu3L2]2+ units are connected with each other by 4,4?-bipy ligands to generate a 2D cation brickwall-like network of [Cu3L2(4,4?-bipy)4]n2n+. These adjacent 2D cation layers are further stacked in a staggered fashion via interlayer stacking interactions to form a 3D supramolecular structure with 1D open square channels, in which the ClO4- counter anions and lattice water molecules are filled. Furthermore, the magnetic property of 1 was also investigated.