Robust, Highly Extensible, and Conformally Self‐Adhesive Ionogels Enabled by Spiderweb‐Inspired Supramolecular Topology

ABSTRACT Ionogels have attracted significant interest in bioelectronics and soft robotics owing to their eco‐friendly stability and adhesion. However, conventional ionogels face an inherent trade‐off between mechanical robustness and both conformality and extensibility: dense crosslinking enhances robustness but compromises skin‐conformal modulus and extensibility, whereas soft, highly extensible networks often suffer from structural failure and poor tensile durability. Herein, we report robust, highly extensible, and conformally self‐adhesive ionogels enabled by a universal, spiderweb‐inspired supramolecular topological strategy. The structural synergy of spiderwebs is mimicked by employing n ‐arm‐PEG‐cucurbit[7]uril topologies as “radial threads” and hydrophilic ionic liquid‐derived P(DMAA‐ co ‐HVIm) chains together with [HMIm]Br as “spiral threads”. By interlocking the polymer chains and compensating for cohesion loss caused by the breaking of weak hydrogen bonds, the host‐guest interaction‐driven topology endows the ionogels with 43.96‐fold stress and 3.24‐fold strain while preserving the skin‐conformal elastic modulus. Maintained in a frequency‐independent critical‐gel‐point state, these recyclable and self‐healing ionogels exhibit exceptional conformally self‐adhesive properties. This structural design bridges the gap between mechanical robustness and skin compliance, offering a highly reliable platform for conformal human‐machine interfaces, even under mechanically demanding scenarios.