Sorption of Ni2+ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni2+ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni2+ at low pH values, whereas no drastic effect of FA/HA on Ni2+ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni2+ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni2+ at different temperatures. The thermodynamic data (ΔH 0, ΔS 0, ΔG 0) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni2+ on rectorite was spontaneous and endothermic. The sorption and species of Ni2+ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni2+ mainly occurred on the surface and at the edge position of Na-rectorite.