Artificial intelligence sensations have aroused scientific interest from electronic conductors to bio-inspired ionic conductors. The conductivity of electrons decreases with increasing temperature, while the ionic conductivity agrees with an Arrhenius equation or a modified Vogel-Tammann-Fulcher (VTF) equation. Herein, thermo-responsive poly(N-isopropyl amide) (PNIPAm) and single-ion-conducting poly(2-acrylamido-2-methyl-1-propanesulfonic lithium salt) (PAMPSLi) were copolymerized via a facile radical polymerization to demonstrate a very intriguing anti-Arrhenius ionic conductivity behaviour during thermally induced volume-phase transition. These smart hydrogels presented very promising scaffolds for architecting flexible, wearable or advanced functional ionic devices.