In recent years, the search for effective antimony adsorption materials has been unyielding. However, the exploration of zeolite imidazolate frameworks (ZIFs) as potential adsorbents, along with the influence of material surface structure and water chemistry on their performance remain under explored. In this study, various molar ratios of Zn2+ and 2-methylimidazole are employed to synthesize three distinct shapes of ZIFs: cube, leaf, and dodecahedron. The experimental outcomes reveal that Leaf-ZIFs, exhibit exceptional adsorption capabilities for Sb(III), the maximum adsorption capacity of Leaf-ZIFs was 57.3 mg g−1. The adsorption kinetics adhere to the pseudo-second-order model, and equilibrium is achieved in approximately 10 h. Additionally, the adsorption isotherm curve is consistent with the Freundlich model. Through comprehensive batch experiments, we thoroughly examined the impact of varying solution pH levels, coexisting ions, and the coexistence of humic acids on the adsorption of Sb(III). The Leaf-ZIFs exhibited remarkable adaptability in neutral, alkaline, and low-concentration heteroionic environments, while demonstrating minimal interference from humic acid present in the solution. Analysis using SEM, XPS, and FTIR techniques revealed that the adsorption mechanism of Leaf-ZIFs primarily involved the partial breakage of the Zn-N bond within the material's structure. This breakage led to the formation of Zn-OH groups, which subsequently reacted with Sb(III) molecules through the -OH groups. The culmination of this process was the formation of Zn-O-Sb bonds, resulting in the effective adsorption of Sb(III) from aqueous solutions.