Imprinted resins have attracted much attention for their high contaminant removal and reuse performance. Chloroacetylated polystyrene resins, polyethyleneimine, epichlorohydrin, and Cu(II) were used as support, functional monomer, cross-linker and template, respectively. The ion-imprinted resins (PS-PEI@SIP) and non-imprinted resins (PS-PEI@NIP) were prepared by the combination of amination reactions and surface ion-imprinting technique. The adsorption processes of Cu(II) with PS-PEI@SIP and PS-PEI@NIP followed pseudo-second-order kinetics. The langmuir isothermal adsorption model was consistent with the adsorption curve, indicating that Cu(II) were uniformly adsorbed on the PS-PEI@SIP surface. Thermodynamic experiments showed that the adsorption of Cu(II) by PS-PEI@SIP was a spontaneous process, and high temperature was favorable for adsorption. In addition, the selectivity of PS-PEI@SIP to Cu(II) was confirmed by multi-component competitive adsorption experiments. When Cu(II) mixed with Ni(II), Zn(II) and Cd(II), the selection coefficients of PS-PEI@SIP for Cu(II) were 31.98, 37.19 and 64.27. The results showed that PS-PEI@SIP had high adsorption capacity and good selectivity for Cu(II) ions in mixed ionic solution, and the adsorption capacity was 89.4 mg·g–1. The simulation wastewater dynamic adsorption experiment showed that the PS-PEI@SIP adsorption column could treat 52.8 BV Cu(II) concentration (C<7.5 mg·g–1), when the influent Cu(II) concentration was 150 mg∙L−1. When 1 mol∙L−1 HCl solution was used for dynamic desorption of PS-PEI@SIP, the desorption rate was more than 92%, indicated that PS-PEI@SIP had good regeneration performance. These results provided basic information for the production of imprinted adsorbent resins.