Enhanced Thermal Conductivity in Tough and Environmentally Resilient Hydrogels

Hydrogels, known for their biocompatibility and responsiveness to external stimuli, are promising candidates for wearable sensors and electronics. However, conventional hydrogels exhibit low thermal conductivity (0.2–0.6 W/m·K), which limits efficient heat dissipation and leads to performance degradation during continuous operation, such as in long‐term wearable health monitors. Moreover, their weak mechanical and environmental stability further constrains their broader applications. In this study, we introduce a multiscale structural engineering approach that leverages the dynamics of pores, crystallization, and hydrogen bonding. Inspired by the design motifs of natural materials such as spider silk, we enhance the thermal conductivity of hydrogels to 1.5 W/m·K. This multiscale structural strategy also improves their mechanical strength and environmental resilience. Our findings provide a blueprint for understanding the process–structure–property relationships and offer a design framework for expanding the practical applications of hydrogels.