Novel chitosan-based granular adsorbents were developed for enhanced and selective separation of heavy metal ions. The research included the synthesis of chitosan hydrogel beads, the cross-linking of the hydrogel beads with ethylene glycol diglycidyl ether (EGDE) in a conventional and a novel amine-shielded method, the functionalization of the chitosan beads through surface grafting of polyacrylamide via a surface-initiated atom transfer radical polymerization (ATRP) method, and the examination of the adsorption performance of the various types of chitosan beads in the removal of heavy metal ions. It was found that chitosan beads were effective in heavy metal adsorption, the conventional cross-linking method improved the acidic stability of the beads but reduced their adsorption capacity, the novel amine-shielded cross-linking method retained the good adsorption capacity while it improved the acidic stability of the beads, and the grafting of polyacrylamide on chitosan beads not only enhanced the adsorption capacity but also provided the beads with excellent selectivity for mercury over lead ions. XPS analyses indicated that the adsorption of metal ions on chitosan beads was mainly attributed to the amine groups of chitosan, the novel amine-shielded cross-linking method preserved most of the amine groups from being consumed by the cross-linking process and hence improved the adsorption capacity of the cross-linked chitosan beads, and the many amide groups from the polyacrylamide grafted on the chitosan beads increased the adsorption capacity and also made possible selective adsorption of mercury ions because the amide groups can form covalent bonds with mercury ions.