Abstract: Objective: To study the relationship between the properties and the structures of the benzimidazole complexes, and explore the preparation method of new antibacterial benzimidazole complexes materials. Methods: Under solvothermal conditions, the assembly of 4, 4'-bis (benzimidazol-1-ylmethy1) biphenyl, isophthalic acid and cobalt, nickel salts resulting two new complexesCo (bbmb)(IPA)·(H₂O)_3n (1) andNi (bbmb)(IPA)(H₂O)·H₂O_n (2). The complexes were characterized by single crystal X-ray structure analyses, thermogravimetric analyses, powder X-ray diffraction and solid-state ultraviolet measurements. Results: Complex 1 had a 2-dimentional sheet framework with S-shaped chains while complex 2 had a 2-dimentional sheet framework constructed from zigzag chains and straight chains. The solid-state UV-Vis absorbance properties were investigated. Conclusions: The structures and properties of the two new benzimidazole complexes are well studied, to provide approaches for the design and exploitation of new benzimidazole complex materials with potential antibacterial activities.