In this paper, a new surface molecular imprinting technique is put forward, and a kind of novel ion-imprinted polymers (IIPs) were prepared through a new approach: firstly functional macromolecule polyethyleneimine (PEI) was grafted onto the surfaces of silica gel particles via the coupling grafting method ('' grafting to '' method) and the composite material PEI/SiO2 with chemical linking was formed; secondly the ionic imprinting was carried out towards the macromolecule PEI grafted on the surface of silica particles using CU2+ or Cd2+ ion as a template, epichlorohydrin (ECH) as a crosslinking agent and by coordination linkage actions, and Cu2+ ion (or Cd2+ ion)-imprinted material IIP-PEI/SiO2 was prepared. The binding characteristics of IIP-PEI/SiO2 for CU2+ ion (or Cd2+ ion) were studied in detail by adopting both static and dynamic methods. The experimental results show that the ion-imprinting material IIP-PEI/SiO2 has specific recognition ability for the template ions, and this character displays mainly in two aspects: (1) it has high affinity for the template ions, its binding amounts for the template ions are much greater than that of the non-imprinted composite material PEI/SiO2, and the adsorption capacity enhances nearly two times compared to PEI/ SiO2; (2) it has excellent selectivity for the template ions, for the IIP-PEI/SiO2 by using Cu2+ as template ion, its selectivity coefficients relative to Zn2+ and Ni2+ are 80.21 and 86.08, respectively, and for the IIP-PEI/SiO2 by using Cd2+ as template ion, its selectivity coefficients relative to Cr3+ and Pb2+ are 77.05 and 88.22, respectively. Besides, the imprinting material IIP-PEI/SiO2 has a fine elution property using HCl solution as eluent. The obtained imprinting material by using the new surface molecular imprinting techniques possesses superexcellent binding property for template molecules or ions because of the distribution of imprinted cavities in a thin polymer layer and smaller diffusion barrier. (c) 2007 Elsevier Ltd. All rights reserved.