Removal of heavy metals from wastewater is of critical importance due to their high toxicity and tendency to accumulate in living organisms. In the present work, performance of a nanofiltration (NF) membrane has been studied to separate cadmium and nickel ions from multicomponent aqueous solutions at different operating conditions. It is observed that the separation of cadmium and nickel ions increases with increase in applied pressure and decreases with increase in feed concentration at a constant feed flow rate. The maximum observed solutes rejection of cadmium and nickel ions are 80.57% and 85.27% for CdCl2-NiCl2-water system and 97.26% and 98.90% for CdSO4-NiSO4-water system, respectively, for an initial feed concentration of 0.005 g/L. This difference in rejection is due to the charge density of the anions. It is also observed that the order of solute rejection sequence is inversely proportional to the diffusion coefficient. The NF membrane is characterized by an irreversible thermodynamics (IT) based Spiegler-Kedem model, coupled with film theory. Boundary-layer thickness and membrane transport parameters are estimated using Levenberg-Marquadt method. The estimated parameters are used to predict the membrane performance and found that the predicted values are in satisfactory agreement with the experimental results. (C) 2010 Elsevier B.V. All rights reserved.