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This review systematically analyzes 99 studies from 2018 to 2025 to elucidate the multiscale interactions among structural topology, material composition, and printing processes that govern the thermal performance of 3D-printed walls. Key findings indicate that thermal conductivity exhibits strong anisotropy (X\u2009&gt;\u2009Y\u2009&gt;\u2009Z) due to layer-by-layer extrusion, while internal configurations\u2014such as cavities, sandwich composites, and bio-inspired structures\u2014significantly enhance insulation and thermal inertia. Material modifications, including the incorporation of phase change materials, waste glass, ETM, and cork, further improve thermal performance, though potential trade-offs with mechanical strength must be considered. Additionally, synergistic fire\u2013thermal design strategies, leveraging fire-resistant composites and layered functional systems, enable simultaneous optimization of thermal resistance and fire safety. Future research directions include the development of thermally adaptive materials, data-driven multiscale optimization, real-time performance monitoring via digital twins, multi-objective design frameworks, and climate-responsive standardization. This review provides a comprehensive framework for designing high-performance, thermally efficient, and fire-safe 3D-printed building envelopes.<\/jats:p>","DOI":"10.1007\/s44213-025-00066-3","type":"journal-article","created":{"date-parts":[[2025,11,24]],"date-time":"2025-11-24T12:32:25Z","timestamp":1763987545000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Multiscale thermal optimization of 3D-printed walls: integrating structure, material, and process with fire-thermal synergy"],"prefix":"10.1007","volume":"3","author":[{"given":"Renyu","family":"Geng","sequence":"first","affiliation":[]},{"given":"Jinming","family":"Jiang","sequence":"additional","affiliation":[]},{"given":"Pengcong","family":"Du","sequence":"additional","affiliation":[]},{"given":"Huiliang","family":"Zhang","sequence":"additional","affiliation":[]},{"given":"Ruiyan","family":"Yu","sequence":"additional","affiliation":[]},{"given":"Weijun","family":"Gao","sequence":"additional","affiliation":[]}],"member":"297","published-online":{"date-parts":[[2025,11,24]]},"reference":[{"key":"66_CR1","doi-asserted-by":"publisher","unstructured":"Abu Qamar MI, Yaghmour E, Wang X, Naito C, Suleiman M, Bocchini P, Fox J, Romero C, Yan L (2024) Use of 3D printed concrete components for thermal energy storage. 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