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A variety of ionic liquid matter has been explored for superior temperature sensing with high-pressure resolution across a broad temperature range. However, it is not so wearable, since its performance is often compromised by environmental humidity or deformations. In this work, we present a linear poly(ionic liquid) elastomer via an in situ polymerization of the carefully selected hydrophobic ionic liquid monomer, tetra- n -butylphosphonium p -styrenesulfonate (P 4444 SS), named as P-P 4444 SS. P-P 4444 SS exhibits remarkable thermosensitivity with a high sensitivity exceeding 8.1%/K and an exceptional resolution of 0.05 °C across an impressive range of −30 to 65 °C. The hydrophobic nature of the ions with assistance of the dense network ensures little water absorption even under 90% humidity condition, giving humidity-independent ionic conduction. The rigid π–π stacking in the polyanion and complex supramolecular cross-linkers within P-P 4444 SS facilitates deformation energy dissipation, resulting in a deformation-insensitive temperature sensor. The temperature error is 0.3 °C under a deformation of 30%, indicating that the P-P 4444 SS sensor is wearable with high reliability and adaptability. A wireless P-P 4444 SS-based temperature sensor was fabricated to detect its wearable applications. These results underscore the importance of structure design for poly(ionic liquids), offering a promising avenue for future technological advancements.
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