The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)_2(H_2PO_4)_2(H_2O)_2 units. The copper atom,located on the crystallographic twofold axis,is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions,and two dihydrogen phosphate oxygen atoms at the axial positions,forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca . 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm,respectively. The two-dimensional networks are stacked parallelly on each other along c -axis to give an extended three-dimensional channel network with an interlayer distance of ca . 0.5030 nm. Crystal data: triclinic,space group P -_1,a =1.0253(2) nm,b =1.4501(3) nm,c =0.79715(16) nm, α =97.91(3)°,β = 90.99(3)° ,γ =85.54(3)°,V =1.1703(4) nm 3,Z =2,R =0.0892,wR =0.2451. The combination of both 4,4’-bipyridine (4,4’-bipy) and dihydrogen phosphate anion ligands with copper (Ⅱ) results in the formation of a novel layered compound Cu (4,4’-bipy) _2 (H_2PO_4) _2 (H_2O) _2. The crystal structure comprises discrete neutral Cu (4,4’-bipy) _2 (H_2PO_4) _2 (H_2O) _2 units. The copper atom, located on the crystallographic twofold axis, is coordinated with two nitrogen atoms of terminal 4,4’-bipy ligands and two water molecules at the equatorial positions, and two dihydrogen phosphate oxygen atoms at the axial positions, forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca. 1.6792 nm × 0.3203 nm and 1.2778 nm × 0.3198 nm, respectively. The two-dimensional networks are stacked parallelly on each other along c -axis to give an extended three-dimensional channel network with an interlayer distance of ca. 0.5030 nm Crystal data: triclinic, space group P-1, a = 1.0253 (2) nm, b Α = 97.91 (3) °, β = 90.99 (3) °, γ = 85.54 (3) °, V = 1.1703 (4) nm 3, and Z = 2, R = 0.0892, wR = 0.2451.