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Ultralight ceramic foam materials with high porosity play an important role in increasingly hi‐tech areas due to the combinative merit of ceramic material and highly porous structure. So far, it remains challenging to fabricate alumina ceramic foams with extremely high porosity and high specific surface area that are comparable to aerogel materials by employing a low cost, eco‐friendly and convenient approach. For the first time, we propose the preparation of aerogel‐like ceramic foams with nanoscale cell wall and unprecedentedly high porosity using boehmite sol as both ceramic source and bubble interface stabilizer, based on sol nanoparticles stabilized foams using sodium lauryl sulfate (SDS) as modifier. The obtained ultra‐stable sol foams allow for the achievement of bulk foams with ultrathin cell wall with thickness in the range of 30‐90 nm, super‐high porosity up to 99%, and large specific surface area of 280 m2/g, which is attributed to the well‐organized assembly of nanoparticles at the liquid/air interfaces. This novel foam material demonstrates excellent adsorption ability for polar volatile organic gases (VOCs) due to its extremely high porosity and large specific surface area. Ultralgiht cellular ceramic foams composed of uniformly assembled nanoparticles with nanoscale cell wall. [ABSTRACT FROM AUTHOR]