Green rusts (GRs), an important intermediate phase during Fe²⁺ oxidation, are commonly associated with various metal cations during their crystallization in soils and sediments, but the effects of metal cations on the formation and transformation of GRs remain unclear. Here, we explored the effects of Mn²⁺, Ni²⁺ and Cu²⁺ on the evolution processes of hydrosulfate green rust (GR2) under various conditions and the mechanism of cations accumulation. The rates of formation and transformation of GR2 decrease in the order of Cu²⁺ > Ni²⁺ > Mn²⁺, and increase with increasing metal cation concentration. When GR2 forms completely, a portion of each cation enters the structure of GR2 by replacing Fe²⁺, and their amount follows the order of Cu²⁺ > Ni²⁺ > Mn²⁺. Under all conditions, the final products are a mixture of lepidocrocite and goethite; a slow mineral Fe²⁺ oxidation rate and a strong surface Fe²⁺ catalytic effects both facilitate the formation of goethite, conversely, favorable to lepidocrocite formation. Additionally, these three cations exhibits different speciation and spatial distribution in lepidocrocite and goethite: Mn mainly exists as Mn(III) and locates in the interior of the crystals; Ni(II) uniformly distributes in the minerals; Cu(II) with minor Cu(I) accumulated at the (sub)surface of the minerals; thus, the complexity of these cations entering the structure of iron oxides decreases in the order of Cu²⁺ > Ni²⁺ > Mn²⁺. These new insights into the interaction between GR2 and trace metal cations improve our understanding of Fe mineralogical properties and the environmental geochemical behaviors of the associated cations in redox alternating soils and sediments.