Four kinds of amino-group-containing chelating fibers were prepared by reacting diethylenetriamine, diethanolamine, diethylamine, and aminopyridine, respectively, with a grafted fiber PVA-g-GMA containing epoxy groups. The gamma-ray preirradiation initiated graft copolymerization of GMA onto PVA fiber, the functionalization of the grafted fiber PVA-g-GMA with amino compounds, and the adsorption properties of the obtained chelating fibers were systematically investigated. It is concluded that with increasing monomer concentration, reaction time, and temperature, the grafting percentage increases significantly. In the functionalization of the grafted fiber, reaction time, temperature, solvent, and amount of amine used greatly influence the reaction. 1,4-Dioxane is a reasonable solvent for the reaction. The chelating fibers present great adsorption amounts and high adsorption rates for Cu2+ ion and Au3+ ion. Among the chelating fibers, the fiber with diethylenetriamine group is the most reasonable chelating fiber for the adsorption of C2+ and Au3+. The chelating fibers present good selectivities for Cu2+ in the solution with Cu2+, Mn2+, Ni2+, Co2+, and Zn2+, while presenting quite high selectivities for Au3+ ion in the solution with Cu2+, Au3+, Zn2+, and Cr3+ ions. The chelating fiber with diethanolamine or diethylamine can reduce the adsorbed Au3+ into metallic gold.