A novel magnetic graphene oxide-based surface imprinted polymer (Fe3O4@GO@IIP) was synthesized by surface imprinting technology to selectively adsorb Ni(II) from aqueous solution. The imprinted polymer was characterized by FT-IR, XRD, SEM, TEM, VSM, TGA and XPS. The results showed the sorbent exhibited good thermal and mechanical stability, which can be quickly separated from the solution by an external magnetic field. The adsorption performance indicated that the prepared imprinted material had a short adsorption equilibrium time (16 min) and a high adsorption capacity (35.31 mg/g) for Ni(II) at the optimal pH of 6.0. The selectivity coefficients of the imprinted material were 17.57, 16.27, 10.86, 14.27 and 17.65 for Ni(II)/Co(II), Ni(II)/Cu(II), Ni(II)/Pb(II) Ni(II)/Cd(II), and Ni(II)/Zn(II), respectively. Reusability studies indicated that the adsorption capacity of the prepared polymer did not decrease significantly after repeated use ten times. Moreover, the adsorption mechanism of Ni(II) by imprinted polymer was also studied. The adsorption process was spontaneous and endothermic, which followed the pseudo-secondary kinetic model and the Langmuir model. The results of the Scatchard model indicated the presence of two Ni(II) strong binding sites on Fe3O4@GO@IIP, where the single-bond O atom of the sulfonic acid group and the N atom of -N-C=O group in AMPS played a dominant role in Ni(II) adsorption, as conformed by both DFT calculations and XPS.