Thermoelectric power generation from waste heat is an important component of future sustainable development. Ion-conducting materials are promising candidates because of their high Seebeck coefficients. This study demonstrates that ionic hydrogels based on imidazolium chloride salts exhibit outstanding Seebeck coefficients of up to 10 mV K-1. Along with their relatively high ionic conductivities (1.6 mS cm(-1)) and extremely low thermal conductivities (similar to 0.2 W m(-1) K-1), these hydrogels have good potential for use in heat recovery systems. The voltage behavior in response to temperature difference (stable or transient) differs significantly depending on the metal electrode material. We evaluated the electrode-dependent temperature sensitivity of the double layer capacitance of these hydrogels, which revealed that the thermally induced polarization of ions at the interface is one of the main contributors to the thermovoltage. Our results demonstrate the potential capability for ion and metal interactions to be used as an effective baseline for exploring ionic thermoelectric materials and devices. The developed thermoelectric supercapacitor exhibits reversible charging-discharging behavior under repeated disconnecting-connecting of an external load with a constant temperature difference, which offers a novel strategy for heat-to-electricity energy conversion from steady-temperature heat sources.