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This review systematically elucidates the underlying photochemical mechanisms\u2014including photoisomerization, photodimerization\/photocleavage, photoredox reactions, and photothermal effects\u2014and critically evaluates three primary design strategies: physical doping, chemical grafting, and host\u2010guest supramolecular recognition, alongside the emerging multi\u2010responsive collaborative design that enables synergistic control through orthogonal stimulus integration. Beyond traditional biomedical applications such as spatiotemporally controlled drug delivery, tissue engineering scaffolds, photodynamic\/photothermal therapy, and biosensing, we highlight the expanding frontiers of PRFHs in soft robotics (artificial muscles, microfluidic valves, intelligent optical devices), information encryption, self\u2010healing materials, switchable adhesives, and environmental remediation, demonstrating their unprecedented versatility. Despite remarkable progress, challenges remain in enhancing biocompatibility and safety (particularly through developing visible\/NIR\u2010driven systems), improving mechanical robustness and response kinetics, and advancing clinical translation via scalable manufacturing and regulatory compliance. Future breakthroughs will likely emerge from integrating artificial intelligence for adaptive feedback control, exploring deep\u2010tissue\u2010penetrating NIR\u2010II excitation, and designing closed\u2010loop systems that combine sensing, actuation, and therapeutic functions, positioning PRFHs as transformative platforms for precision medicine, advanced bionics, and sustainable environmental technologies.<\/jats:p>","DOI":"10.1002\/asia.70987","type":"journal-article","created":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T04:37:49Z","timestamp":1789101469000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Photo\u2010Responsive Functional Hydrogels: Mechanism, Design, and Application"],"prefix":"10.1002","volume":"21","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-9998-7569","authenticated-orcid":false,"given":"Sheng\u2010Yu","family":"Zhu","sequence":"first","affiliation":[{"name":"Henan Key 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