A novel recoverable magnetic Cd(II) ion-imprinted polymer was synthesized on the surface of silica-coated Fe3O4particles via the surface imprinting technique and chemical grafting method. The resulting polymer was used as a highly efficient adsorbent for the removal of Cd(II) ions from aqueous solutions. The adsorption experiments revealed that Fe3O4@SiO2@IIP had a maximum adsorption capacity of up to 29.82 mg·g−1for Cd(II) at an optimal pH of 6, with the adsorption equilibrium achieved within 20 min. The adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm adsorption model. Thermodynamic studies showed that the adsorption of Cd(II) on the imprinted polymer was spontaneous and entropy-increasing. Furthermore, the Fe3O4@SiO2@IIP could rapidly achieve solid–liquid separation in the presence of an external magnetic field. More importantly, despite the poor affinity of the functional groups constructed on the polymer surface for Cd(II), we improved the specific selectivity of the imprinted adsorbent for Cd(II) through surface imprinting technology. The selective adsorption mechanism was verified by XPS and DFT theoretical calculations.