A facile route for preparation of poly(tert-butyl acrylate) covalently wrapped silica nanoparticles (SiO2/PtBA) was demonstrated by the single-electron transfer mediated living radical polymerization (SETLRP). Firstly, the surface of silica nanoparticles (SiO2 NPs) was modified with (3-aminopropyl) trimethoxysilane. Subsequently, a SET-LRP initiator was immobilized on the amine functional SiO2 NPs by the Ugi reaction of 2-bromo-2-methylpropionic acid, benzaldehyde, and 1-pentyl isocyanide. The SET-LRP of tert-butyl acrylate was carried out by using copperwire and PMDTA as a catalyst system. The grafting of PtBA on the surface of SiO2 NPs was investigated by FT-IR, XRD, TGA, and TEM analysis. Gel permeation chromatography analysis illustrated the molecular weight of PtBA increased with monomer conversion. The hydrolysis of the PtBA part yielded hydrophilic poly(acrylic acid) decorated SiO 2 NPs, which showed high colloidal stability.