Waste heats of an internal combustion engine (ICE) are recovered by a dual-loop organic Rankine cycle (DORC). Thermodynamic performance analyses and optimizations are conducted with 523.15–623.15 K exhaust gas temperature (Tg1). Cyclopentane, cyclohexane, benzene, and toluene are selected as working fluids for high-temperature loop (HTL), whereas R1234ze(E), R600a, R245fa, and R601a are selected as working fluids for low-temperature loop (LTL). The HTL evaporation temperature, condensation temperature, and superheat degree are optimized through a genetic algorithm, and net power output is selected as the objective function. Influences of Tg1 on system net power output, thermal efficiency, exergy efficiency, HTL evaporation temperature, HTL condensation temperature, HTL superheat degree, exhaust gas temperature at the exit of the HTL evaporator, heat utilization ratio, and exergy destruction rate of the components are analyzed. Results are presented as follows: the net power output is mainly influenced by HTL working fluid. The optimal LTL working fluid is R1234ze(E). The optimal HTL evaporator temperature increases with Tg1 until it reaches the upper limit. The optimal HTL condensation temperature increases initially and later remains unchanged for a cyclopentane system, thus keeping constant for other systems. Saturated cycle is suitable for cyclohexane, benzene, and toluene systems. Superheat cycle improves the net power output for a cyclopentane system when Tg1 is 568.15–623.15 K.