A well-defined molecularly imprinted polymer nanospheres with excellent specific recognition ability was prepared on Fe3O4 nanoparticles via the combination of click chemistry and surface-initiated reversible addition fragmentation chain transfer (RAFT) polymerization and using Tetrabromobisphenol A as template. Concretely, Fe3O4 nanoparticles were prepared by solvothermal method and then modified by 4-vinylbenylchloride through distillation-precipitation, which makes azide groups easily introduced on the surface of magnetic nanoparticles to form the relatively large amount of benzyl chloride groups. With high efficiency, alkyne terminated RAFT chain transfer agent were then immobilized onto the surface of Fe3O4 by means of click chemistry, which is Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The highly uniform imprinted thin film was finally fabricated on the surface of RAFT agent modified Fe3O4 nanoparticles. The binding results demonstrated that as-prepared imprinted beads exhibited remarkable molecular imprinting effects to the template molecule, fast rebinding kinetics and an excellent selectivity to compounds with similar configuration. (C) 2017 Elsevier B.V. All rights reserved.