Chelated coppers, such as CuII-EDTA, are characteristically refractory and difficult to break down because of their high stability and solubility. CuII–EDTA sequestration by structural Fe(II) (Fe(II)) was investigated intensively in this study. Up to 101.21mgCu(II)/gFe(II) was obtained by Fe(II) in chelated copper sequestration under near neutral pH condition (pH 7.70). The mechanism of CuII-EDTA sequestration by Fe(II) was concluded as follows:3CuII–EDTA+7Fe(II)+9H2O →Cu(0)↓+ Cu2O↓(the major product)+2Fe2O3·H2O↓+3FeII–EDTA +14H+Novel results strongly indicate that CuII reductive transformation induced by surface Fe(II) was mainly responsible for chelated copper sequestration. Cu(0) generation was initially facilitated, and subsequent reduction of Cu(II) into Cu(I) was closely combined with the gradual increase of ORP (Oxidation-Reduction Potential). Cu-containing products were inherently stable, but Cu2O would be reoxidized to Cu(II) with extra-aeration, resulting in the release of copper, which was beneficial to Cu reclamation. Concentration diminution of CuII–EDTA within the electric double layer and competitive adsorption were responsible for the negative effects of Ca2+, Mg2+. By generating vivianite, PO43− was found to decrease surface Fe(II) content. This study is among the first ones to identify the indispensible role of reductive decomplexation in chelated copper sequestration. Given the high feasibility and reactivity, Fe(II) may provide a potential alternative in chelated metals pollution controlling.