This paper investigates the effectiveness of two commercial micron zero-valent irons (mZVIs) in removing Sb(V) from antimony mine wastewater. The wastewater contains a range of complex components and heavy metal ions, including As(V), which can impact the removal efficiency of mZVI. The study aims to provide insights into actual working conditions and focuses on influencing factors and standard conditions. The results demonstrate that mZVI can reduce Sb(V) concentration in the mine wastewater from 3875.7 μg/L to below the drinking water standard of 5 μg/L within 2 h. Adding a small amount of mZVI every 30 min helps to maintain a high removal rate. The study confirms the existence of a reduction reaction by changing the atmospheric conditions of the reaction, and the addition of 1,10-phenanthroline highlights the important role of active Fe(II) in the adsorption and removal of Sb(V) by mZVI. Additionally, the paper presents an innovative experimental method of acid treatment followed by alkali treatment, which proves the interfacial reaction between mZVI and Sb(V). Overall, the study demonstrates that the removal of Sb(V) by mZVI entails a dual function of reduction and adsorption, highlighting the potential of mZVI in repairing Sb(V) in antimony mine wastewater.