To investigate the effect of heat loss reduction due to thermal insulator and thermal interface resistance due to multi-layer structure in order to improve the efficiency of a thermoelectric device, a thermoelectric concrete brick was fabricated using a unileg n-type CaMnO3 thermoelectric module inside. CaMnO3 thermoelectric materials were synthesized by starting materials CaCO3 and MnO2 to produce a unileg n-type CaMnO3 module. Thermoelectric concrete brick consisted of two types: I-layer brick (one layer of concrete thermal insulator) and III-layer brick (three layers of different concrete insulators). The occurring temperature difference, electric current and voltage on the CaMnO3 module and thermoelectric concrete brick were measured in closed and open circuits. The temperature difference, thermal distribution, and output voltage when applying constant temperatures of 100, 200 and 400 °C were measured. Computer simulations of the Finite Element Method (FEM) were performed to compare with the experimental results. The trends of the temperature difference and the output voltage from the experimental and computer simulations were in good agreement. The results of the temperature difference during the hotter side temperature of 200 °C exhibited the temperature difference along the vertical direction of the thermoelectric concrete bricks for both types of the III-layer brick of 172 °C and the I-layer brick of 132 °C are larger than that of the CaMnO3 TEG module without using a thermal concrete insulator of 108 °C. The thermoelectric concrete bricks of the III-layer brick type of 27.70 mV displayed output voltage results being higher than those of the I-layer brick of 26.57 mV and the CaMnO3 TEG module without using a thermal concrete insulator of 24.35 mV. Thermoelectric concrete brick of the III-layer brick type displayed higher electric generation power than the I-layer brick and the CaMnO3 TEG module. Additionally, the results exhibited the capability of thermoelectric concrete brick in the III-layer brick model for electric generation power based on the temperature difference. The TEG concrete brick of I-layer concrete covering the series–parallel combination circuit of 120 modules of the unileg n-type CaMnO3 was constructed and then embedded on the outer surface of the furnace. During the maximum hotter side temperature of 580 °C of the concrete brick, the temperature difference between the hotter side and the cooler side of the brick occurred at 365 °C and the maximum output voltage was obtained at 581.7 mV.