In this study, the reductive transformations of 2-nitrophenol (2-NP) by interfacial complex systems of Fe(Ⅱ) associated with kaolinite and montmorillonite respectively were systematically investigated. The results showed that surface-bonded Fe(Ⅱ) species on the minerals can effectively improve the rate of reductive transformations. The reduction reactions of 2-NP over the complex systems can be described by the pseudo first-order kinetics. The rate constant (k) was increased with the pH, initial Fe(Ⅱ) concentration and reaction temperature. Moreover, 2-NP removal efficiency can reach 100% within 4.0 h by the presence of Fe(Ⅱ)/kaolinite system under the conditions of pH 6.7 and temperature 25℃, initial concentrations of 3.0 mmol/L Fe(Ⅱ) and 0.022 mmol/L 2-NP as well as the dose of kaolinite at 4.0 g/L. Similarly, when the solution pH increased from 6.0 to 7.3, the transformation for 2-NP removal was also clearly enhanced by the presence of Fe(Ⅱ)/montmorillonite system, but the conditions with a lower pH and a lower initial Fe(Ⅱ) concentration were quite not favorable for montmorillonite to effectively catalyze 2-NP to be reduced by Fe(Ⅱ), and the performance was even lower than that of kaolinite. This may be ascribed to montmorillonite having a higher cation-exchange capacity. Therefore, the difference in speciation of adsorbed Fe(Ⅱ) is the intrinsic reason for controling the 2-NP reductive transformation in the mentioned mineral interfacial reduction systems.