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Low efficiency of the thermoelectric generation system hinders its application in the conventional industries and living areas. In order to improve the system efficiency by enhancing the heat transfer between high-temperature heat source and thermoelectric modules, the optimal structure parameters of porous annular flame cover are obtained by detailed numerical simulation. Based on this, a prototype of the high-temperature thermoelectric generator has been built. The experimental data and numerical results show that the optimized burner brings higher temperature heat source and more uniform temperature distribution on the hot side of the thermoelectric modules. The output power and efficiency of the system increase by 611.80% and 388.35% respectively.