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Surface ion-imprinted in combination with sol-gel process was applied to synthesis a new Pb(Ⅱ)-imprinted polymer for selective separation and enrichment of trace Pb(Ⅱ) from aqueous solution. The prepared material was characterized by using the infrared spectra, X-ray diffractometer, and scanning electron microscopy. The batch experiments were conducted to study the optimal adsorption condition of adsorption trace Pb(Ⅱ) from aqueous solutions on Pb(Ⅱ)-imprinted polymer. The equilibrium was achieved in approximately 4.0 h, and the experimental kinetic data was fitted the pseudo second-order model better. The maximum adsorption capacity was 22.7 mg/g, and the Langmuir equation fitted the adsorption isotherm data. The results of selectivity experiment show that selectively adsorbed rate of Pb(Ⅱ) on Pb(Ⅱ)-imprinted polymer is higher than all other studied ions. Desorption conditions of the adsorbed Pb(Ⅱ) from the Pb(Ⅱ)-imprinted polymer were also studied in batch experiments. The prepared Pb(Ⅱ)-imprinted polymer was shown to be promising for the separation and enrichment of trace Pb(Ⅱ) from water samples. The adsorption and desorption mechanisms were proposed.