Two new CuII coordination polymers, namely [Cu2(BDC)2(L)4 (H2O)2]•14H2O(1) and [Cu1.5(BTC)(L)1.5(H2O)0.5] • 2H2O( 2), where L = 1,1’-(1,4-butanediyl)bis(imidazole), BDC = 1,4- benzenedicarboxylate, and BTC = 1,3,5-benzenetricarboxylate, have been synthesized at room temperature. Complex 1 exhibits an unusual, square-planar, four-connected 2D 264 net, which has been predicated by Wells. Interestingly, three types of water clusters, namely (H2O)6,( H2O)8, and (H2O)10, are observed in the hydrogen-bonded layers constructed by the BDC ligands and water molecules. The BTC anion in compound 2 is coordinated to the CuII cation as tetradentate ligand to form a (66)2(426484)2(64810) net containing three kinds of nonequivalent points. Thermogravimetric analyses (TGA) and IR spectra for 1 and 2 are also discussed in detail.