In this article, we studied the sorption properties of poly(ethyleneimine) coated on silica gel for metal ions with impact on the environment, such as Zn(II), Cd(II), Hg(II), and Pb(II). The experiments were carried out by batch procedure and the effects of pH, concentration, and temperature were evaluated. In addition, the selectivity was studied for binary, ternary, and quaternary metal ion mixtures. Mercury and lead showed promising results, achieving higher than 65% of sorption after only 1 h of contact. Under competitive conditions, resin presented high selectivity toward Hg(II) reaching 91 and 87% of retention respect to total amount of ions for binary and quaternary mixtures, respectively. The effect of time on Pb(II) and Hg(II) sorption was studied by batch procedure and the experimental data were adjusted to pseudo-first-order, pseudo-second-order, and intra-particle diffusion models. Pseudo-second-order model presented good agreement for Pb(II) sorption, while pseudo-first-order model fits better to Hg(II) sorption. Intra-particle diffusion model showed that sorption process is controlled mainly by film diffusion.