Hollow microspheres of nickel hydroxide and nickel oxide were prepared with as-synthesized PS/Ni(OH)2 composite particles by sacrificing core method, respectively. The composite particles were synthesized by deposition of the Ni(OH)2 nanoflakelets formed by the hydrolysis of nickel nitrate onto the surfaces of polystyrene (PS) particles. The effects of different concentrations of nickel salt and urea on the deposition of the nanoflakelets of nickel hydroxide were studied. It was found that the uniform nanoflakelets were deposited on the polystyrene particles under the conditions of the 4╳10-3 M nickel salt and 0.667M urea. Compared with the directly calcinating of composite particles, Integral hollow microspheres of nickel hydroxide were attained by removal of cores of polystyrene in composite particles with toluene and NiO hollow microspheres by calcinating of these Ni(OH)2 hollow spheres in oven at 600°C for 2h.