In recent, there are tremendous efforts to apply co-generation concept in automobile to improve its thermal efficiency. The co-generation is basically a simple Rankine Cycle that uses the waste heat from the engine exhaust and coolant for heat source. In spite of developed nano technology and advance material science, the bulky co-generation system is still a big concern in automotive application. Therefore, the system should be effectively designed not to add much weight on the vehicle, but the capacity of the waste heat recovery should be still large. With such a goal in mind, the system thermal efficiency was investigated in terms of the system operation condition and working fluid. This paper provides a direction for the optimal design of the automotive co-generation system.