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Polystyrene microspheres with an average diameter of 55 μm were prepared by suspension polymerization via oxidation of the monomer by ammonium persulfate. Poly-3-aminophenylboronic acid was grafted onto the surfaces of the polystyrene microspheres to form polystyrene/poly-3-aminophenylboronic acid core- shell micospheres. The samples were characterized by scanning electron microscopy, Raman spectroscopy, X-ray photo-electron spectroscopy and nitrogen adsorption/desorption method. The results show that poly-3-aminophenylboronic acid was successfully grafted to the surfaces of the polystyrene microspheres by aromatic ring electron-pairing interaction. The surfaces of the core-shell micro-spheres possessed a porous structure, with the average pore diameter of 30.2 nm and the BET surface area of 193.26 m2/g.