In this paper, a waste heat recovery compound system for series hybrid electric vehicles is established. The existing components of vehicle air conditioning are used in the organic Rankine cycle (ORC) to realize miniaturization. The waste heat recovery compound system is constructed using GT-SUITE, and the objective of the analysis is to increase the power output and engine thermal efficiency increase ratio (ETEIR). The effects of the expander speed, pump speed, working fluid mass flow rate, and working fluid type on the waste heat recovery compound system are analyzed. The simulation results show that the optimal schemes for the ORC system and compound system corresponding to the expander speed and pump speed are 1000 pm, 2500 rpm, 1200 rpm, and 2500 rpm, respectively. Compared with the ORC system, the maximum power output of the compound system with the same working fluid in three states (1500 rpm, 2500 rpm, and 3500 rpm) of the engine is increased by 21.67%, 24.05%, and 28.23%, respectively. Working fluid supplies of 0.4 kg/s, 0.4 kg/s, and 0.6 kg/s in the three engine states are also considered the best solutions. The working fluid R1234yf and R1234ze are the preferred choices for a waste heat recovery compound system, which have a high system power output and ETEIR and are environmentally friendly.