Bio‐Inspired Rigid‐Flexible Synergistic Nanofibrous Textiles for Mechanically Robust Radiative Cooling

ABSTRACT Passive daytime radiative cooling (PDRC) textiles offer an efficient pathway for personal thermal management. However, the inherent conflict between optical performance and mechanical robustness remains a formidable challenge. Although elastomer‐based electrospun nonwovens serve as a potential solution, they typically necessitate high nano‐filler loading for sufficient reflectance, which inevitably weakens interfacial bonding, leading to performance degradation and even structural failure during cyclic deformation. Herein, inspired by spider silk, we propose a filler‐free biomimetic rigid‐flexible synergy strategy regulated by dynamic hydrogen bonding. Via coaxial electrospinning, a robust TPU@PVDF‐HFP film (RTPF) comprising a thermoplastic polyurethane (TPU) core and a polyvinylidene fluoride‐co‐hexafluoropropylene (PVDF‐HFP) sheath is engineered. The RTPF demonstrates outstanding mechanical strength (10.17 MPa) and elongation (301.34%), exhibiting superior mechanical and spectral stability with a mere 10.53% residual strain and 1.58% degradation after 1000 cycles at 30% strain. Attributed to high solar reflectance (96.2%) and long‐wave infrared emittance (92.5%), the RTPF achieves an average/maximum temperature reduction of 21.3/25.4°C on uncovered heated‐pad under 950 W·m − 2 irradiation. Remarkably, it exhibits exceptional stability against rigorous washing and extreme environments (high/low temperatures and acid/alkali conditions). This bioinspired design achieves a synergistic enhancement of optical performance and mechanical robustness, paving the way for long‐term wearable cooling materials.