The narrow particle size distribution of poly (vinyl silicone) microspheres were prepared by the hydrolysis-polycondensation method with vinyl silane (VTMS) as raw materials. And the influences of pH value, oil/water ratio on the morphology, particle size and distribution of the microspheres were studied. The results shows that the particle size of microspheres decrease with the increasing of the PH value of polymerization, and the particle size has no specific linear relationship with the PH value of hydrolysis reaction, while the oil-water ratio is smaller, single particle size distribution is more narrow, more uniform distribution.