Abstract: Emulsions with high monodispersity were prepared through a hydrolysis-polymerization process. The influence of process parameters like emulsifier HLB, reaction time, emulsifier content and monomer content were studied. Then, the emulsion was coated as a template and organic silicone was used as a shell layer to obtain hollow microspheres. The emulsions and microspheres were characterized by Zetasizer Nano ZS90, SEM, TEM, EDS and FTIR. The results showed that highly monodispersed emulsions could be prepared at room temperature for 6 h. By changing the amount of emulsifier and original monomer, the particle size of the emulsion could be turned from 346 nm to 472 nm. Then, monodisperse hollow mi-crospheres with regular morphology could be obtained when the mass fraction of the emulsifier was less than 0.003% by using the emulsion as a template, and the main component of hollow microspheres was organic silicone. By comparing with hard templating method, the preparation process was relatively simple and the template could be removed by washing with ethanol.