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Inspired by this principle, porous organic cages (POCs), featuring well\u2010defined intrinsic cavities, solution processability, and high chemical tunability, have emerged as versatile molecular platforms for multiscale materials engineering. This concept highlights representative examples in which POCs act as modular, shape\u2010persistent building blocks within hierarchical assemblies, and elucidates how their confined cavities, solubility, and structural modularity enable the rational construction of sophisticated materials systems. At the molecular level, POCs function as enzyme\u2010mimetic hosts that encapsulate and stabilize metal clusters (MCs) within discrete cavities. Benefiting from their structural tunability, POCs can also serve as bulky building blocks for integration into extended frameworks (e.g., COFs, MOFs, and supramolecular frameworks), as well as for the construction of nested host\u2010in\u2010host architectures and well\u2010ordered multiscale crystalline materials. Such hierarchical assembly integrates structural advantages across length scales by preserving intrinsic porosity while introducing efficient mass and electron transport pathways, thereby enabling enhanced separation and catalytic performance. By translating bioinspired design principles into synthetic materials, these systems offer a programmable route towards multifunctional platforms.<\/jats:p>","DOI":"10.1002\/chem.71212","type":"journal-article","created":{"date-parts":[[2026,6,2]],"date-time":"2026-06-02T16:45:13Z","timestamp":1780418713000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Recent Advances in Hierarchical Porous Organic Cages: From Discrete Structure to Integrated Assemblies"],"prefix":"10.1002","author":[{"given":"Muhammad Asad","family":"Ziaee","sequence":"first","affiliation":[{"name":"MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering Beijing Institute of Technology  Beijing P.R. 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