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(H2PO4)2(H2O)2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)2(H2PO4)2(H2O)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) nm3, Z=2, R=0.0892, wR=0.2451.