In situ silica filling of styrene grafted natural rubber (ST-g-NR) was carried out by using sol-gel reaction of tetraethoxysilane (TEOS). The effects of concentration of catalyst and reaction temperature on the in situ silica content were investigated. ST-g-NR was synthesized via an emulsion polymerization using cumene hydroperoxide (CHPO) and tetraethylene pentamine (TEPA) as initiators. The synthesized ST-g-NR was characterized by a Fourier Transform Infrared Spectroscopy (FTIR) and Proton Nuclear Magnetic Resonance Spectroscopy (1H NMR). The content of in situ silica generated in ST-g-NR matrix was determined by Thermogravimetry Analysis (TGA). In situ silica up to 50 parts per hundred rubbers by weight (phr) was successfully filled in the ST-g-NR matrix. The silica content increased with the increase of n-hexylamine concentration. However, the effect of reaction temperature was insignificant to silica content.