AbstractA thermocell generates thermopower from a temperature difference (ΔT) between two electrodes. The converse process of thermocells is an electrochemical Peltier effect, which creates a ΔT on the electrodes by applying an external current. The Seebeck coefficient (S_e) of the electrochemical system is proportional to the entropy change of the redox reaction; therefore, a redox system having a significant entropy change is expected to increase the S_e. In this study, a thermoresponsive polymer having a redox‐active moiety, poly(N‐isopropyl acrylamide‐co‐N‐(2‐acrylamide ethyl)‐N′‐n‐propylviologen) (PNV), is used as the redox species of a thermocell. PNV²⁺ dication undergoes the coil–globule phase transition upon the reduction to PNV⁺ cation radical, and a large entropy change is introduced because water molecules are freed from the polymer chains. The S_e of PNV thermocell drastically increased to +2.1 mV K⁻¹ at the lower critical solution temperature (LCST) of PNV. The entropy change calculated from the increment of S_e agrees with the value evaluated by differential scanning calorimetry. Moreover, the electrochemical Peltier effect is observed when the device temperature is increased above the LCST. This study shows that the large entropy change associated with the coil–globule phase transition can be used in electrochemical thermal management and refrigeration technologies.