The film-forming polyacrylate/silica core-shell nanocomposite particles with octamethylcyclotetrasiloxane (D 4 ) were successfully synthesized via aqueous emulsion polymerization in the presence of a glycerol-functionalized nano silica sol. The ringopening polymerization of D 4 and the reaction with the glycerol-functionalized nano silica particles before emulsion polymerization was the key procedure in this process. Transmission electron microscopy results showed that more nano silica particles tended to coat on the polyacrylate particles surface after the nano silica sols were modified with D 4 . The silica aggregation efficiency was increased from 90.9 to 98.6% when the amount of D 4 used in the system was varied from 0 to 8.0 wt %. The transparency of the nanocomposite films was not compromised after D 4 was incorporated into the system. The films of the nanocomposite particles with or without D 4 both exhibited superior abrasive resistance. Furthermore, the water resistance and hydrophobicity of the films of these particles with D 4 were also improved significantly.