Bioinspired Swelling‐Deswelling Strategy Unlocks Synergistic Molecular Solar Thermal‐Fabric Systems for Personal Thermal Management

Abstract Molecular solar thermal (MOST) fabrics represent a transformative approach to personal thermal management (PTM) through their capability to control the storage and release of solar energy. Nevertheless, the critical challenge of interfacial incompatibility between MOST molecules and fabrics persists, resulting in compromised robustness and suboptimal energy conversion efficiency. Here, inspired by the salt absorption‐secretion mechanism of Atriplex centralasiatica , an innovative swelling‐deswelling strategy tailored for hollow aerogel fibers (HAFs) is developed, creating a synergistically promoted MOST‐fabric system (SPMFS) with concurrent enhancements in mechanical robustness and photothermal performance. During the swelling‐deswelling process, thermoplastic polyurethane (TPU) chains undergo reorganization into a densified network, while the simultaneous secretion of azobenzene (Azo) forms dense, uniform monocrystalline layers. The resultant SPMFS exhibits notable mechanical improvements, with a 48% increase in breaking strain and 129% enhancement in tensile strength. Equally striking are its photothermal capabilities, achieving an enhanced photo‐charging and photo‐discharging (>94% photoconversion) alongside a uniformly distributed high energy density of 7.5 kJ m −2 . Moreover, the SPMFS enables programmable rapid thermal management, showcases impressive durability under long‐term washing, cyclic stretching, and rubbing, and realizes controllable photothermal physiotherapy. This bioinspired strategy lays the groundwork for next‐generation wearable PTM systems and establishes a framework for future PTM device design