A novel coordination polymer {[Cu(L-1)(L-2)(H2O)].5H2O}(n) (1), where L-1 = 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 Pna2(1), which belongs to the crystal class mm2, with a = 9.0521(18), b = 15.401(3), and c 17.141(3) Angstrom, alpha = beta = gamma = 90degrees, V = 2389.7(8) Angstrom(3), and Z = 4. The complex 1 composing a porous supramolecular architecture displays unprecedented four-connected topology of an 86 net in coordination polymer chemistry. Thermal gravimetric analysis (TGA) and X-ray powder diffraction (XRPD) patterns for 1 are discussed in detail.