Redox-stimulated host–guest chemistry was applied for the electrochemical Peltier effect, which is a heat transportation phenomenon observed in redox-active electrolytes. The refrigeration capability was enhanced up to 70%. By the addition of alpha-Cyclodextrin (α-CD) into I−/I3− aqueous solution, the amount of heat transported from the cathode side to the anode side was observed. The enhancement of the heat transportation was derived from the elimination heat of I3− from α-CD associated with the shift of host–guest equilibrium caused by the exhausting of I3− by the reduction. This is the first report that utilized the stimuli-responsive supramolecular interaction for heat transportation.