Thermal insulation under extreme conditions requires materials that can withstand complex thermomechanical stress and retain excellent thermal insulation properties at temperatures exceeding 1,000 degrees Celsius1–3. Ceramic aerogels are attractive thermal insulating materials; however, at very high temperatures, they often show considerably increased thermal conductivity and limited thermomechanical stability that can lead to catastrophic failure4–6. Here we report a multiscale design of hypocrystalline zircon nanofibrous aerogels with a zig-zag architecture that leads to exceptional thermomechanical stability and ultralow thermal conductivity at high temperatures. The aerogels show a near-zero Poisson’s ratio (3.3 × 10−4) and a near-zero thermal expansion coefficient (1.2 × 10−7 per degree Celsius), which ensures excellent structural flexibility and thermomechanical properties. They show high thermal stability with ultralow strength degradation (less than 1 per cent) after sharp thermal shocks, and a high working temperature (up to 1,300 degrees Celsius). By deliberately entrapping residue carbon species in the constituent hypocrystalline zircon fibres, we substantially reduce the thermal radiation heat transfer and achieve one of the lowest high-temperature thermal conductivities among ceramic aerogels so far—104 milliwatts per metre per kelvin at 1,000 degrees Celsius. The combined thermomechanical and thermal insulating properties offer an attractive material system for robust thermal insulation under extreme conditions.