In order to further study the coordination reaction rules and properties of organic ligands containing benzimidazole with Zn(Ⅱ), a new one-dimensional coordination polymer {［Zn(AMBI)(H₂O)SO₄］·0.5H₂O}<sub>n has been synthesized by the reaction of zinc(Ⅱ) sulfate heptahydrate with the bidentate ligand 2-aminomethyl-1H-benzimidazole (AMBI) and characterized by elemental analysis, IR, UV spectrum, TG and single-crystal X-ray diffraction. The thermal stability is studied. X-ray single-crystal structure analysis shows that the colorless block crystal of the title complex belongs to monoclinic system, space group C2/c. In the complex, the Zn(Ⅱ) is coordinated by two N atoms from one AMBI ligand, two O atoms from SO^2-₄ ion and one O atom from water in a distorted square pyramidal coordination geometry. The structure of the title complex exhibits an infinite chain-like structure through bridging SO^2-₄ anion. The hydrogen-bonding and π…π interactions extend the complex into quasi 3D networks. Through the structure study on the supra-molecular complex, it′s further understood about how the structure of the ligand and non-covalent interactions, such as hydrogen bonding and π…π stacking, influence the topological structures of supra-molecular compounds. This study has important reference value for rational selection of organic ligands and synthesis of coordination polymers with novel structures.