In this study, the effect of Fe, Fe, and Mn dose, solution pH, reaction temperature, background water matrix (i.e., inorganic anions, cations, and natural organic matters (NOM)), and the kinetics and mechanism for the reaction system of Fe(VI)/Fe, Fe(VI)/Fe, and Fe(VI)/Mn were investigated systematically. Traces of Fe, Fe, and Mn promoted the DCF removal by Fe(VI) significantly. The pseudo-first-order rate constant (k) of DCF increased with decreasing pH (9-6) and increasing temperature (10-30 °C) due to the gradually reduced stability and enhanced reactivity of Fe(VI). Cu and Zn ions evidently improved the DCF removal, while CO restrained it. Besides, SO, Cl, NO, Mg, and Ca almost had no influence on the degradation of DCF by Fe(VI)/Fe, Fe(VI)/Fe, and Fe(VI)/Mn within the tested concentration. The addition of 5 or 20 mg L NOM decreased the removal efficiency of DCF. Moreover, FeO and Fe(OH), the by-products of Fe(VI), slightly inhibited the DCF removal, while α-FeOOH, another by-product of Fe(VI), showed no influence at pH 7. In addition, MnO and MnO, the by-products of Mn, enhanced the DCF degradation due to catalysis and superposition of oxidation capacity, respectively. This study indicates that Fe and Fe promoted the DCF removal mainly via the self-catalysis for Fe(VI), and meanwhile, the catalysis of Mn and the effect of its by-products (i.e., MnO and MnO) contributed synchronously for DCF degradation. Graphical abstract ᅟ.