AbstractAdsorption of precious metal ions from aqueous solutions has earned great concern recently due to environmental protection factor and the value of precious metals. In this article, a novel adsorbent silica gel microspheres encapsulated by amino functionalized polystyrene (SG‐PS‐NH2) has been synthesized, and the adsorption selectivity and the dynamic adsorption properties of SG‐PS‐NH2 for Cu(II), Ag(I), and Au(III) has been investigated. The results displayed that SG‐PS‐NH2 had excellent adsorption for Au(III)/Ag(I) in binary ion systems, especially in the systems of Au(III)‐Zn (II), Au(III)‐Ni(II), and Ag(I)‐Zn(II). The dynamic adsorption showed that the adsorption capacities of SG‐PS‐NH2 for Cu(II), Ag(I), and Au(III) increased with the prolonging of contact time, and the affinity order of three metal ions adsorbed by of SG‐PS‐NH2 is Au(III) > Ag(I) > Cu(II), which is inversely correlated with their electronegativities. The regeneration capacities of SG‐PS‐NH2 were investigated by using the eluent solution of 0.5% thiourea in 1 mol/L HCl, and it is found that the changes of the adsorption capability are relatively small after several cycles of adsorption–desorption. Thus, silica gel encapsulated by polystyrene containing amino groups (SG‐PS‐NH2) is favorable and useful for the removal of precious metal ions because it is eco‐friendly and easier to reuse. The comparison of SG‐PS‐NH2 with other adsorbents suggests that SG‐PS‐NH2 have great potential applications in environmental protection and the recovery of precious metals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010