Acid mine drainage is highly acidic and contains large quantities of Fe and heavy metal elements. Thus, it is important to promote the transformation of Fe into secondary iron minerals that exhibit strong heavy-metal removal abilities. Using simulated acid mine drainage, this work analyzes the influence of monovalent cations (K + , NH 4 + , and Na + ) on the Fe 2+ oxidation and total Fe deposition efficiencies, as well as the phases of secondary iron minerals in an Acidithiobacillus ferrooxidans system. It also compares the Cr(VI) (K 2 Cr 2 O 7 ) and As(III) (As 2 O 3 ) removal efficiencies of different schwertmannites. The results indicated that high concentrations of monovalent cations (NH 4 + ≥ 320 mmol/L, and Na + ≥ 1600 mmol/L) inhibited the biological oxidation of Fe 2+ . Moreover, the mineralizing abilities of the three cations differed (K + > NH 4 + > Na + ), with cumulative Fe deposition efficiencies of 58.7%, 28.1%, and 18.6%, respectively [n(M) = 53.3 mmol/L, cultivation time = 96 h]. Additionally, at initial Cr(VI) and As(III) concentrations of 10 and 1 mg/L, respectively, the Cr(VI) and As(III) removal efficiencies exhibited by schwertmannites acquired by the three mineralization systems differed [n(Na) = 53.3 > n(NH 4 ) = 53.3 > n(K) = 0.8 mmol/L]. Overall, the analytical results suggested that the removal efficiency of toxic elements was mainly influenced by the apparent structure, particle size, and specific surface area of schwertmannite.