Copolymerized vinyl/phenylsilsesquioxane microspheres were prepared by the sol-gel polymerization method from phenyltrimethoxysilane (PTMS) and vinyltrimethoxysilane (VTMS). The microsphere size was from 0.8 μm to 2.7 μm. Effects of the reaction parameters, such as NH4OH concentration, the ratio of oil to water (O/W) and monomer ratio on microsphere size, shape and distribution were investigated. The results indicate that the preferred preparation conditions are NH4OH concentration in 0.02 ∼ 1.28 wt%, ratio of O/W from 1/3 to 1/50 in hydrolytic co-condensation reaction. With the increasing of NH4OH concentration and PTMS/VTMS ratio and decreasing of O/W ratio, the microsphere size is decreased. Finally, FT-IR measurement was used to characterize the structure of the copolymerized vinyl/phenylsilsesquioxane microspheres.