By molecular design, a new ion surface-imprinting technique was set up based on surface-initiated graft-polymerization, and arsenate anion surface-imprinted material with high performance was prepared for the first time. A redox initiating system was constituted by the amino groups on the surface-modified silica gel particles and the ammonium persulphate in the solution. The cationic monomer 2-methacryloyloxyethyl-trimethyl ammonium chloride (DMC) was used as functional monomer and N,N'-methylenebisacrylamide (MBA) was used as cross-linker. In the solution, the monomer molecules were arranged around the template ion, arsenate anion, via ion exchange action, and then the arsenate anion surface-imprinting was carried out along with the surface-initiated graft-polymerization of DMC and MBA, forming arsenate anion surface-imprinted material IIP-PDMC/SiO2. The experimental results show IIP-PDMC/SiO2 possesses specific recognition selectivity and excellent, binding affinity for arsenate anion. The selectivity coefficients of IIP-PDMC/SiO2 for arsenate anion are 8.814 and 7.898 relative to chromate and nitrate ions, respectively.