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The combined thermo-generator and organic rankine cycle (TEG-ORC) used in exhaust heat recovery of internal combustion engine (ICE) is analyzed theoretically. Only about one third of the total energy released from fuel combustion is converted into useful work in engines, while the remaining energy goes into ambient environment, among which exhaust gas possesses high-grade thermal energy. Most of previous studies on energy recovery from engines have focused on exhaust heat recovery by ORC. However, if the heat is exchanged directly with high-temperature exhaust gas, organic working fluid would resolve with its lower decomposition temperature, and this is extremely harmful to ORC system. To avoid this phenomenon and utilize waste heat, preliminary thermoelectric modules are used to lower exhaust temperature and to generate electricity simultaneously.