A chemical process involves polymerization within microspheres, whereas a physical process involves the dispersion of polymer in a nonsolvent. Nano-sized monodisperse microspheres are usually prepared by chemical processes such as water-based emulsions, seed suspension polymerization, nonaqueous dispersion polymerization, and precipitation polymerizations. Polymerization was performed in a four-necked, separate-type flask equipped with a stirrer, a condenser, a nitrogen inlet, and a rubber stopper for adding the initiator with a syringe. Nitrogen was bubbled through the mixture of reagents for 1 hr. before elevating the temperature. Functional silane (3-mercaptopropyl)trimethoxysilane (MPTMS) was used for the modification of silica nanoparticles and the self-assembled monolayers obtained were characterized by X-ray photoelectron spectroscopy (XPS), laser scattering system (LSS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental analysis (EA), and thermogravimetric analysis (TGA). In addition, polymer microspheres were polymerized by radical polymerization of γ-mercaptopropyl modified silica nanoparticles (MPSN) and acrylamide monomer via precipitation polymerization; then, their characteristics were investigated. From the elemental analysis results, it can be concluded that the conversion rate of acrylamide monomer was 93% and that polyacrylamide grafted to MPSN nanospheres via the radical precipitation polymerization with AAm in ethanol solvent. The microspheres were successfully polymerized by the 'graft from' method.