A novel coordination polymer [[Cu(L(1))(L(2))(H(2)O)].5H(2)O](n) (1), where L(1) =1,1'-(1,4-butanediyl)bis(imidazole) and L(2) = m-phthalate anion, has been obtained by using an unusual crystallization process. It crystallizes in the orthorhombic space group Pna2(1), which belongs to the crystal class mm2, with a = 9.0521(18), b = 15.401(3), and c = 17.141(3) A, alpha = beta = gamma = 90 degrees, V = 2389.7(8) A(3), and Z = 4. The complex 1 composing a porous supramolecular architecture displays unprecedented four-connected topology of an 8(6) net in coordination polymer chemistry. Thermal gravimetric analysis (TGA) and X-ray powder diffraction (XRPD) patterns for 1 are discussed in detail.