Aiming to reduce thermal energy loss at the cold side of a thermoelectric generator (TEG) module during thermoelectric conversion, a thermoelectric energy conversion system for heat recovery with a water-cooling energy exchange circuit was devised. The water-cooling energy exchange circuit realized sufficient recovery and reuse of heat accumulated at the cold side of the TEG, reduced the danger of heat accumulation, improved the stability and output capacity of thermoelectric conversion, and provided a low-cost and high-yield energy conversion strategy in energy conversion and utilization. Through the control variable method to adjust the heat generation of the heat source in the thermoelectric conversion, critical parameters (e.g., inner resistance of the TEG, temperatures of thermoelectric modules, temperature differences, output current, voltage, power, and efficiency of thermoelectric conversion) were analyzed and discussed. After using the control variable method to change the ratio of load resistance and internal resistance, the impacts of the ratio of load resistance to inner resistance of the TEG on the entire energy conversion process were elaborated. The results showed that the maximum value of output reached 397.47 mV with a current of 105.56 mA, power of 41.96 mW, and energy conversion efficiency of 1.16%. The power density of the TEG module is 26.225 W/m2. The stability and practicality of the system with a water-cooling energy exchange circuit were demonstrated, providing an effective strategy for the recovery and utilization of heat energy loss in the thermoelectric conversion process.