All‐Solid‐State Hydrophobic Ionic‐Conductor with Large Strain Self‐Recovery and High Toughness for Multi‐Scenario Sensing Applications

All‐solid‐state ion‐conductive elastomers (ICEs) have shown promising prospects in the field of flexible electronics and are becoming a research hotspot in both academic and industrial circles. However, these shortcomings of low mechanical robustness, large residual strain, and susceptibility to hydrolytic failure still significantly hinder their applications in multi‐scenario and multi‐modal sensing. This paper reports a novel strategy for fabricating all‐solid‐state hydrophobic poly(ionic liquid)‐based conductive elastomers (PILEs) using acryloyloxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide ([ATAC][TFSI]). Soft acrylate monomers modulate electrostatic interactions and hydrophobic interactions to achieve energy dissipation network construction and improves hydration resistance and toughness. The results show that the PILEs exhibit excellent mechanical properties (maximum elongation at break, toughness, and tensile strength up to 820.4%, 27.53 MJ m−3, and 8.05 MPa, respectively). Thanks to the dynamic energy dissipation network, elastomers also demonstrate excellent self‐recovery properties under large‐strain (400%) stretching, which provides a foundation for stabilizing the sensing output. In addition, PILEs possess ionic conductivity and extreme environmental stability. The AT‐80% sensor designed in this study demonstrates repeatability and rapid response/recovery characteristics, enabling multimodal ion sensing for applications such as underwater communications, diving attitude monitoring, marine biology research, respiration monitoring. This study presents novel concepts for the development of flexible sensors applied to complex scenarios.