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Here, we establish a facile and general strategy to overcome this limitation via directional freezing\u2010assisted cryo\u2010polymerization. The anisotropic growth of ice crystals imposes spatial confinement during network formation, driving dense chain packing and stabilizing amide\u2010based emissive clusters. Such structural confinement suppresses nonradiative decay and enables a robust CTE effect even at ultrahigh water content (\u223c90 wt%), effectively overcoming the long\u2010standing challenge of hydration\u2010induced quenching. The resulting polyacrylamide hydrogel exhibits stable blue emission, structural stability, excellent resistance to water\u2010induced quenching, and mechanical softness with elasticity and shape programmability, enabling rewritable and multilevel information encryption. More broadly, this work demonstrates that stable intrinsic luminescence in water\u2010rich soft materials can be achieved through structural confinement rather than molecular modification, providing a general design principle for CTE systems and opening new opportunities for integrating optical functionality with structural programmability in soft materials.<\/jats:p>","DOI":"10.1002\/anie.8034701","type":"journal-article","created":{"date-parts":[[2026,6,20]],"date-time":"2026-06-20T09:14:04Z","timestamp":1781946844000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Freezing\u2010Induced Spatial Confinement During Cryo\u2010Polymerization Enables Stable Intrinsic Luminescence in Hydrogels"],"prefix":"10.1002","volume":"65","author":[{"given":"Shumiao","family":"Li","sequence":"first","affiliation":[{"name":"State Key Laboratory of Organic\u2010Inorganic Composites Beijing University of Chemical Technology  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