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Automotive exhaust-based thermoelectric generator (TEG), which effectively converts exhaust thermal energy into electrical energy, can gradually improve the utilization efficiency of energy. The heat exchanger of TEG is one of the most important components for heat transfer, so as to realize energy saving and emission reduction. Hence, its configuration and thermal performance should be intensively studied. In this paper, a new configuration of heat exchanger, whose heat transfer area is regular octagon, is designed in comparison with the pervious rectangle one. In order to improve average temperature and thermal distribution uniformity, typical CFD software named FLUENT is used to simulate the multi-coupling of temperature - fluid - solid, and the temperature distribution on heat transfer area is gained. Moreover, the temperature distribution will be analyzed to evaluate the merits and weaknesses of configuration and thermal performance.