A method is described for the selective separation and extraction of cadmium-lead from aqueous solutions by tuning the pH value between 1.0 and 7.0. A modified nano-active silica sorbent was loaded with 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide hydrophobic ionic liquid, [Bmim+Tf2N] and used in this work. The pH value was found to play a significant role in the sorption capacity of Cd(II) and Pb(II). In pH 1.0, the metal capacity values were characterized as 1.40 and 0.30mmol g1 for Cd(II) and Pb(II), respectively. In pH 7.0, Cd(II) and Pb(II) switched their capacity values to 0.65 and 1.00mmol g1, respectively. An anion exchange mechanism was proposed in solution with pH 1.0 for exchange of chloroanionic cadmium species by [Tf2N]. The sorptive separation processes of Cd(II) and Pb(II) were studied and evaluated under the influence of various controlling factors. The potential applications of modified nano-silica sorbent for selective sorptive removal and separation of Cd(II) from Pb(II) in water samples was successfully accomplished by adjusting the pH value of the contact solution between 1.0 and 7.0. The results of this study indicated an efficient extraction behavior of the two examined metal ions.