A flat wall-like thermoelectric generation system is developed for applications in exhaust heat of kilns. The design of the whole experimental setup is presented. The essential performance of the thermoelectric generation system is tested, including open-circuit voltage, output power, and system conversion efficiency. The results illustrate that, when heat source insulation is not considered, the system conversion is efficient at hot-side temperatures between 120°C and 150°C. In addition, the nonuniformity of heat transfer is found to significantly affect the power-generating ability of the system. System-level simulation is carried out using a quasi-one-dimensional numerical model that enables direct comparison with experimental results. The results of both experiment and simulation will provide a foundation to improve and optimize complex thermoelectric generation systems.