| Summary: | Abstract To date, the restricted capability to fabricate ceramics with independently tailored nano‐ and macroscopic features has hindered their implementation in a wide range of crucial technological areas, including aeronautics, defense, and microelectronics. In this study, a novel approach that combines self‐ and digital assembly to create polymer‐derived ceramics with highly controlled structures spanning from the nano‐ to macroscale is introduced. Polymerization‐induced microphase separation of a resin during digital light processing generates materials with nanoscale morphologies, with the distinct phases consisting of either a preceramic precursor or a sacrificial polymer. By precisely controlling the molecular weight of the sacrificial polymer, the domain size of the resulting material phases can be finely tuned. Pyrolysis of the printed objects yields ceramics with complex macroscale geometries and nanoscale porosity, which display excellent thermal and oxidation resistance, and morphology‐dependent thermal conduction properties. This method offers a valuable technological platform for the simplified fabrication of nanostructured ceramics with complex shapes.
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