High‐performance thermal protective composites with lightweight, micro‐ ablation and high‐efficient thermal insulation are urgently required for thermal protection systems in advanced hypersonic speed vehicles. However, the practical applications of thermal protective composites have long been hampered by the main issues such as low mass residual rate and poor long‐term antioxidation of the matrix in high‐temperature aerobic environments. Here, we report a novel silica‐polybenz oxazine (SiO2‐PBO) aerogels with interpenetrated networks, possessing the ability to antioxidation, thermal insulation, and flame‐retardant properties. The resulting SiO2‐PBO aerogels exhibit low density (0.25 g/cm3), low thermal conductivity (0.035 W/(m·K)), and superior peak heat release rate value (15.3 W/g). Moreover, the mass residual rate is up to 70.46 wt% in the N2 atmosphere and remains 57.83 wt% despite existing in the air atmosphere and experiencing the highest temperature of 800°C. Briefly, SiO2‐PBO aerogels as‐prepared could be a potential matrix for a new gene ration of high‐performance thermal protective composites in the future.

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