A novel coordination polymer {[Cu(L1)(L2)(H2O)] •5H2O}n (1), where L1 = 1,1’-(1,4-butanediyl) bis (imidazole) and L2 = m-phthalate anion has been obtained by using an unusual crystallization process. It crystallizes in the orthorhombic space group Pna21, which belongs to the crystal class mm2, with a = 9.0521(18), b = 15.401(3), and c = 17.141(3) Å, α = β = γ= 90°, V = 2389.7(8) Å3, and Z = 4. The complex 1 composing a porous supramolecular architecture displays unprecedented four-connected topologyof an 86 net in coordination polymer chemistry. Thermal gravimetric analysis (TGA) and X-ray powder diffraction (XRPD) patterns for 1 are discussed in detail.