The development of adhesive materials with excellent heat resistance is urgently to ensure the performance of advanced equipment at extreme environments up to 1500 ℃. In the present work, a novel hybrid zirconium-silicone resin (ZAS resin) was synthesized via the addition of zirconium n-propoxide (ZTP) as a structural control component in copolycondensation with alkoxysilanes. Thermal properties revealed that the addition of Zr significantly improved the heat resistance. The residual weight was increased by 168.2%, from initial 31.58 wt% to 84.71 wt%, at 1000 ℃ under Argon atmosphere. A suitable phase diagram showing the structural crystal transformation under high temperature was proposed. The bonding strength of ZAS33 resin increased 296.1% and 92.8% at room temperature and after ablation at 1200 ℃ for 0.5 h, respectively. The underlying mechanisms accounted for the improvements were discussed and correlated to the zirconium content. The resin exhibited extraordinary storage stability at least 6 months, which greatly broadened the application prospects of ZAS resin as high-temperature resistant bonding materials.