Thermocells are garnering increasing attention as a promising thermoelectric technology for harvesting low-grade heat. However, their performance is often limited by the scarcity of high-performance redox couples that possess both high thermopower and rapid redox kinetics. This work addresses this challenge by leveraging our recently developed copper (I/II) (Cu+/Cu2+) redox couple. We significantly enhance the performance of Cu-based liquid thermocells by integrating a thermosensitive crystallization process with etched carbon cloth electrodes, achieving synergistic improvements in thermodynamic and kinetic performance. The thermosensitive crystallization process establishes a persistent Cu2+ concentration gradient, boosting the thermopower from 1.47 to 2.93 mV K−1. Moreover, the etched carbon cloth electrodes provide a larger electroactive surface area and demonstrate a higher current density. Consequently, the optimized Cu+/Cu2+ system achieved an exceptional normalized power density Pmax (ΔT)−2 of 3.97 mW m‒2 K−2. A thermocell module comprised of 20 cells directly power various electronic devices at a temperature difference of 40 K. This work successfully exhibits potential of Cu+/Cu2+ redox couple in thermoelectric conversion and introduces a valuable redox couple for high-performance thermocells.