Flexible Eutectogel Sensors Enabled by Metal–Ligand Dynamics for Ultrasensitive, Broad‐Range, and Robust Temperature Sensing

Abstract Flexible temperature sensors capable of accurately detecting and transmitting thermal stimuli from biological, environmental, and electronic sources are essential for electronic skins, human–machine interfaces, and hazard monitoring systems. However, developing intrinsically soft yet thermally sensitive materials remains elusive, since most current strategies integrate rigid thermo‐responsive elements into flexible substrates, compromising sensitivity, mechanical compliance, and scalability. Herein, we introduce a coordination‐driven molecular design strategy leveraging metal–ligand dynamics within tailored deep eutectic solvent (DES) systems to construct P(NIPAM‐co‐VA)/LiTFSI/ZnCl 2 eutectogels. This dynamic coordination network empowers the eutectogels with exceptional thermal sensitivity and inherent mechanical softness. The resulting eutectogel sensor achieves an ultrahigh temperature coefficient of resistance (TCR) of −77.18% °C −1 , ultra‐fine temperature resolution of 0.05 °C, excellent linearity (R 2 = 0.996), and robust thermal durability from −10 to 120 °C. This 130 °C wide operating range enables applications from cold‐chain monitoring to thermal runaway detection in advanced electronic systems, facilitating scalable, intelligent thermal management. Furthermore, an intelligent audio–visual dual‐alert system is demonstrated for real‐time detection and early warning of abnormal temperature changes in cold‐chain scenarios. Collectively, this work establishes metal–ligand‐coordinated eutectogels as a versatile platform for flexible temperature sensors with high sensitivity, wide operational range, and practical utility.