Nine new coordination polymers, namely, [Mn-2(L)(H2O)(4)]center dot H2O (1), [Cd(L)(0.5)(H2O] (2), [Zn-5(L)(2)(mu(3)-O)(2)(H2O)(4)]-2H(2)O (3), [Zn-4(L)(2)(mu(3)-O)(2)[Zn(H2O)(5)]center dot 2H(2)O (4), [Zn-2(L)(biim-4)(0.5)(H2O)(3)]center dot H2O (5), [Cd-2(L)(bpy)(H2O)]center dot 2H(2)O center dot 0.5(CH3CH2OH) (6), [Cu-2(H2L)(2)(bpy)(2)] (7), (Cu-2(L)(bpy)(H2O)] (8), and [Cu-2(L)(bpy)(1.5)(H2O)(2.5)] (9), where H4L = 1,2,3,4-benzenetetracarboxylic acid, biim-4 = 1,1'-(1,4-butanediyl)bis(imidazole), and bpy = 4,4'-bipyridine, have been synthesized under hydrothermal conditions. Compound 1 displays a rare trinodal (3,4,7)-connected (4(2).6)(4(5).6)(4(7).6(8).8(6)) topology. 2 possesses an alpha-Po net. 3 is a novel 3D framework based on pentanuclear Zn-II clusters. By adjustment of the pH values of the reaction mixture of 3 with a Na2CO3 Solution, a structurally different compound, 4, was obtained, which exhibits a 3D porous framework with the [Zn(H2O)(6)](2+) cations located in the channels. 5 is an unusual example of a trinodal (3,5)-connected network with a Schlafli symbol of (4(2).6)(6(2).8)(4(2).6(2).8(5).10), whereas 6, containing tetranudear Cd-II clusters, shows a rare (4,6)-connected (4(4).6(2))(2)(4(4).6(10).8) topology. 7 exhibits a unique polythreading network, while 8 displays a scarce trinodal (3,4,5)-connected self-penetrating network. 2 In 3 comparison with 8, the chiral compound 9 possesses an unprecedented tetranodal (2,4)-connected (7)(7(5).11)(6(2).7(3).8)(2)(6.7(4).10)(2) topology. The effects of the carboxylate ligands, the pH values, the reaction temperatures, the central metals, and the neutral ligands were elucidated. The IR spectra, thermogravimetric analysis, and luminescent properties for the compounds were also investigated.