Eight new coordination polymers, [Zn(L)Cl] n (1), [Zn 2 (L) under hydrothermal conditions and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Complexes 1, 2, and 7 display a two-dimensional (2D) layer structure. Complex 3 presents a complicated 2D layer structure with paddle-wheel units, which exhibits an interesting (3,4,6)-connected 3-nodal new topological net with the point symbol of (3Complex 4 is a 2-nodal (3,5)-connected 2D bilayer structure with the gek1 topological net and the point symbol of (3•4•5)(3 2 •4•5•6 2 •7 4 ). Complex 5 shows a self-penetrating three-dimensional (3D) framework based on pentanuclear clusters, which features an intriguing (3,3,4,4,12)-connected 5-nodal new topological net with the point symbol of (4•6 2 ) 2 (4 2 •6 4 ) 4 (4 3 ) 2 (4 8 •6 34 •8 22 •10 2 ). Complex 6 features a 2-fold interpenetrating (3,4)-connected 3D framework with the ins topological net and the point symbol of (6 3 )(6 5 •8). Complex 8 is a new (4,4,5,6)-connected 3D network built up by a linear Cd 3 (COO) 6 trinuclear cluster with the point symbol of (4 2 •6 3 •8) 2 (4 3 •6 3 ) 2 (4 4 •6 4 •8 2 ) 2 (4 8 •6 6 •8). The diverse structures indicate that rational adjustment of the second ligand, the pH value, and counteranion are good methods to further design metal−organic compounds with new structures and properties. In addition, the thermal stabilities and photoluminescence properties of 1−8 were also studied.