A series of superhydrophobic poly(methacryloxy-propyltrimethoxysilane, MPTS-b-2,-2,3,3,4,4,4-heptafluorobutyl methacrylate, HFBMA)-grafted silica hybrid nanoparticles (SiO2/PMPTS-b-PHFBMA) were prepared by two-step surface-initiated atom transfer radical polymerization (SI-ATRP). Under the adopted polymerization conditions in our previous work, the superhydrophobic property was found to depend on the SI-ATRP conditions of HFBMA. As a series of work, in this present study, the effects of polymerization conditions, such as the initiator concentration, the molar ratio of monomer and initiator, and the polymerization temperature on the SI-ATRP kinetics and the interrelation between the kinetics and the surface properties of the nanoparticles were investigated. The results showed that the SI-ATRP of HFBMA was well controlled. The results also showed that both the surface microphase separation and roughness of the hybrid nanoparticles could be strengthened with the increase of the molecular weight of polymer-grafted silica hybrid nanoparticles. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 174-183, 2011