A series of zinc(II) compounds, [Zn-2(btca)(2)(im)(2)]center dot(DMA) (1; H(2)btca = benzotriazole-5-carboxylate acid, im = imidazole, and DMA = N,N-dimethylacetamide), [Zn(btca)(im)]center dot(DMF) (2; DMF = N,N-dimethylformamide), [Zn-2(btca)(2)(tmdpy)]center dot 2(DMF)center dot 5(H2O) [3; tmdpy = 1,3-di(4-pyridyl)propane], and [H2N(CH3)(2)](2)[Zn-3(btca)(4)]center dot(DMF) (4), have been successfully synthesized via rational control of experimental conditions. Single-crystal X-ray diffraction analyses indicate that compounds 1 and 2 are isomers, and both of them exhibit two-dimensional structures with the same uninodal 3-connected fes topology. Additionally, the three-dimensional (3D) structure of 3 was obtained by using tmdpy instead of an im ligand under synthesis conditions similar to those of compound 2. Interestingly, compound 3 presents a pillared-layer structure with a (3,4)-connected (4.8(2).10(3))(4.8(2)) topology. When 4,4'-bipyridine was used to replace tmdpy, the assembly between Zn2+ ions and H(2)btca ligands produced a chiral 3D framework of 4. Furthermore, compound 4 showed a new (3,4)-connected topology with a vertex symbol of (4.6.8(4))(2)(4.6.8)(4.8(2))(6.8(2))(2)(6.8(5)). A comparison of all compounds suggested that the structural diversity of the compounds could be tuned by altering the auxiliary ligand. In addition, the photoluminescent properties of compounds 1-4 were measured.