The undesirable inherent natural characteristics of wood, such as low mechanical strength, flammability, and hygroscopicity, limit its potential applications in the thermal insulation industry. Overcoming these disadvantages can greatly expand the application scope of wood. A new attempt at wood modification, the directional-freezing-assisted in situ sol–gel strategy, was used to obtain wood–silica composite aerogels with the unique multi-level ordered porous structure of wood. This method enables silica nanoparticles to successfully replace lignin and facilitates the formation of strong hydrogen bonds between the silica and cellulose molecules. This results in improved mechanical properties for the composite with a density similar to that of natural wood but a mechanical strength that can be up to five times greater. The thermal conductivity coefficient is also reduced to 0.032 W (m·K)−1 compared to 0.066 W (m·K)−1 for natural wood. This aerogel composite exhibits improved fire resistance and hygroscopicity, with a decomposition temperature increase of approximately 45 °C compared to natural wood. Additionally, the composite demonstrates self-extinguishing behavior, with the structure remaining intact after combustion, and thus enhanced fire resistance. Simultaneously, the enhanced aerogel composite hydrophobicity, with water contact angle of up to 120°, is beneficial to a prominent thermal insulation performance in a high-humidity environment. The successful synthesis of wood-based composite aerogels provides a new and innovative approach for the utilization of wood resources in the thermal insulation industry.

The use of energy-saving materials is an effective strategy for decreasing energy consumption and carbon emission. Wood is a type of biomass material with a natural hierarchical structure, which results in its high thermal insulation. It has been widely used in construction. However, developing wood-based materials without flammability and dimensional instability is still a challenge. Herein, we developed a wood/polyimide composite aerogel with a well-preserved hierarchical pore structure and dense hydrogen bonds inside, resulting in its excellent chemical compatibility and strong interfacial interactions between its two components. This novel wood-based composite was fabricated by removing most hemicellulose and lignin from natural wood, followed by the fast impregnation using an ‘in situ gel’ process. The introduction of polyimide into delignified wood substantially improved its mechanical properties, with the compression resistance being improved by over five times. Notably, the thermal conductivity coefficient of the developed composite was approximately half that of natural wood. Furthermore, the composite exhibited excellent fire-retardancy, hydrophobicity, thermal insulation, and mechanical properties. This study provides a novel method for wood modification, which not only aids interfacial compatibility between wood and polyimide but also retains the properties of the two components. The developed composite can effectively reduce energy consumption, making it promising for practical and complex thermal insulation applications.