Thermally stable methylsilicone xerogel monoliths were prepared by sol-gel technology with methylsilicone oligomer as precursor and titania nanoparticles as filler. The effects of titania doping and heating temperature on the structure, morphology, and hydrophobic property of xerogels were investigated. The structural evolution under thermal treatment showed that the blank methylsilicone monolith was crushed after 300 A degrees C treatment, but the samples reinforced by titania could retain the intact structure after 500 A degrees C treatment. Thermogravimetric analysis results certified that the thermal degradation of methylsilicone was resisted due to incorporation of TiO2. Fourier transform infrared spectra and Si-29 nuclear magnetic resonance results showed that Si-CH3 unit still existed in the reinforced samples, compared with the complete transformation of Si-C to Si-O in the blank methylsilicone after 500 A degrees C treatment. Thus, the hydrophobic property was preserved and certified by measurement of contact angle.