Highly porous aerogels based on renewable materials that possess structural functionality are appealing for sustainable energy regulation and harvesting. Achieving structural anisotropy provides advantageous directional diffusion and mechanical strength, however, introduces great engineering challenges, such as complex, costly, and time-consuming processing. Direct use of wood, where nanocellulose is favorably orientated, offers the opportunity of forming low-cost, scalable, and eco-friendly aerogels. This thesis explores a new type of nanostructured wood material design by filling the empty wood space with cellulosic aerogel structures based on its intrinsic biopolymers. The structure control is achieved through selective reassembly of the cell wall nanocomponents by cell wall partial dissolution and regeneration. The resultant structures, named integrated wood aerogels, show a unique combination of high specific surface area and strength due to partial retention of the wood hierarchical structure and formation of mesoporous nanofibrillated networks occupying the lumen. Different chemical systems are investigated, including DMAc/LiCl, ionic liquid (IL), and aqueous NaOH, and the processing-structure-property relationships are investigated. DMAc/LiCl is successfully used as proof of concept for integrated wood aerogel formation, but moisture sensitivity and toxicity of the system hinder further development. The IL [MTBD][MMP] is developed to solve the issues and to improve the structure control in cell wall dissolution and regeneration. An aqueous NaOH system advances the integrated cellulosic wood aerogel preparation further, considering low cost and greener chemistry. Wood composition, lignin in particular, is critical to the processing and final properties of the integrated wood aerogel. The influence of lignin content is investigated based on IL and NaOH systems. The influence of processing (such as chemical system, time and temperature) on the structure and properties (e.g. porosity, specific surface area, mechanical performance, thermal conductivity and charge density) of the aerogels are studied. Ascribing to the structure-property profile, the application of the integrated aerogel for efficient thermal insulation is demonstrated. Inspired by the water uptake in plants, high-performing pH-responsive wood power generators are formed based on water evaporation-induced electricity. The integrated aerogel structure greatly increases the solid/liquid interphase while allowing excellent mass diffusion. The methodologies presented in this thesis for selective nanoscale reassembly of the wood cell wall pave the way for advanced wood nanostructure control. The integrated wood aerogel structure reported here provides a universal material platform for advanced material design, such as a self-sustaining wood power generator. The facile and scalable processing contribute toward sustainable high-performing bioaerogels which can compete with fossil-based materials. urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-319629