The hybrid microspheres with polystyrene core coated by titania nanoparticles were prepared by miniemulsion polymerization, and the as-prepared samples were characterized by SEM, XRD, TG-DTA, XPS, and SPS techniques. TiO2 (nanoparticles experienced two processes of phase transition, i.e., amorphous to anatase and anatase to rutile at the calcining temperature range from 400 to 1000 C. The phase transformation temperature of TiO)(2) (hybrid microspheres from anatase to rutile was increased by about 300 C due to the blocking function of calcined polymer remainder. SPS results present that the band-gap of hybrid microspheres is 3.2-3.4 eV, which is larger than that of pure TiO)(. The maximum intensity of the SPS signal is about 3 times larger for the hybrid material as compared to the pure TiO)(. In addition, the photocatalytic degradation rate of TiO)(2)(2)(2) (hybrid microspheres was 15% faster than that of pure TiO)(2) in the experiment of the photocatalytic degradation of methyl orange.