A novel polyglycidylmethacrylate (PGMA) microspheres with high adsorption capacity of Cr(VI) was prepared by cerium(IV) initiated graft polymerization of tentacle-type polymer chains with amino group on polymer microspheres with hydroxyl groups. The micron-sized PGMA microspheres were prepared by a dispersion polymerization method and subsequently modified by ring-opening reaction to introduce functional hydroxyl groups. The polymer microspheres were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results indicated that the polymer microspheres had an average diameter of 5 mu m with uniform size distribution. The free amino group content was determined to be 5.13 mmol.g(-1) for g-PGMA-NH2 microspheres by potentiometric and conductometric titration methods. The Cr(VI) adsorption results indicated that the graft polymerization of tentacle-type polymer chains on the polymer microspheres could produce adsorbents with high adsorption capacity (500 mg.g(-1)). The polymer microsphcres with grafted tentacle polymer chains have potential application in large-scale removal of Cr(VI) in aqueous solution.