Ionic liquid–based ionogels emerge as promising candidates for efficient ionic thermoelectric conversion due to their quasi-solid state, giant thermopower, high flexibility, and good stability. P-type ionogels have shown impressive performance; however, the development of n-type ionogels lags behind. Here, an n-type ionogel consisting of polyethylene oxide (PEO), lithium salt, and ionic liquid is developed. Strong coordination of lithium ion with ether oxygen and the anion-rich clusters generated by ion-preferential association promote rapid transport of the anions and boost Eastman entropy change, resulting in a huge negative ionic Seebeck coefficient (−15 millivolts per kelvin) and a high electrical conductivity (1.86 millisiemens per centimeter) at 50% relative humidity. Moreover, dynamic and reversible interactions among the ternary mixtures endow the ionogel with fast autonomous self-healing capability and green recyclability. All PEO-based ionic thermoelectric modules are fabricated, which exhibits outstanding thermal responses (−80 millivolts per kelvin for three p-n pairs), demonstrating great potential for low-grade energy harvesting and ultrasensitive thermal sensing.