In this paper, a Rankine cycle test system is established to recover exhaust energy from a 2.0 L gasoline engine. Experiments on the system’s performance are carried out under various working conditions. The experimental results indicate that the recovery power of the expander is strongly related to the load and speed of the gasoline engine. It is found that when the output power of the gasoline engine is 39.8⁻76.6 kW, the net power of the expander is 1.8⁻2.97 kW, which is equivalent to 3.9%⁻4.9% of the engine power. The performance simulation shows that the mass flow rate, power output, and isentropic efficiency of the piston expander are directly determined by the intake valve timing. Selecting a suitable intake valve timing can optimize the performance of the expander. The simulation results show that a 1 kW increment in power can be obtained only by selecting an optimum intake open timing. The experimental results further verify that the single-valve piston expander, because of its small dimensions, simple structure, and high speed, is appropriate, and has great potential for energy recovery of gasoline engine exhaust and has good prospects for engineering applications.