Directly Sunlight‐Chargeable Core‐Shell Azobenzene Fabric via Coaxial Electrospinning with Tunable Personal Thermal Management

Personal thermal management (PTM) represents an energy‐efficient strategy for maintaining human thermal comfort. Solar‐driven PTM technologies are particularly attractive due to their sustainability. Azobenzene‐based molecular solar thermal systems (Azo‐MOSTs) stand out for their ability to efficiently convert photon energy into storable thermal energy and release it on demand. However, fabricating a wearable Azo‐MOST that simultaneously ensures leak‐free encapsulation and direct sunlight charging remains a significant challenge. Herein, a core‐shell structured Azo fabric is developed via coaxial electrospinning, using a tetra ‐ ortho ‐halogenated Azo derivative as the core that capable of visible‐light‐induced solid‐to‐liquid transformation and a transparent poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) layer as the shell. The fabric achieves a high E ‐to‐ Z conversion of 78% under direct natural sunlight, the highest reported for azo fabric to date. It also exhibits excellent wearability, including good air permeability, strong hydrophobicity (water contact angle >130°) and stable heat release performance after repeated charging‐discharging cycles (10 circles), washing (25 h), or bending (1000 times). Upon 430 nm light irradiation, the fabric shows rapid and stable heat release, reaching a surface temperature of 61.1 °C within 5 min. Practical demonstrations confirm its utility: it provided localized heating up to 64.2 °C on a mannequin and maintained safe skin‐contact temperatures (50–52.3 °C) on a human subject at room temperature. Moreover, the fabric retained substantial heating performance under low‐temperature conditions (0–10 °C), certifying its adaptability for personal thermal regulation in varied environments. This work presents a leakage‐free, sunlight‐chargeable core‐shell Azo‐based textile that effectively bridges molecular photothermal storage with wearable functionality, offering a robust platform for on‐demand PTM.