Solar-driven cascade ejector system can not only promote the utilization reliability of the solar energy, but also improve the performance of solar energy systems. This paper proposes a novel solar-driven cascade ejector system which integrates a solar ejector heat storage subsystem with R290 as refrigerant and a transcritical CO2 ejector-expansion refrigeration subsystem. The conventional and advanced exergy analysis methods are utilized to investigate the system’s exergetic performance, and explore the interactions among the system components and their improvement potential. The effects of compressor efficiency, area ratio and efficiency of ejectors on the exergetic performance of system and components are investigated. The analysis results show that the transcritical CO2 ejector-expansion refrigeration subsystem has higher exergy efficiency and its components have small exogenous exergy destruction. The endogenous exergy destruction and the avoided exergy destruction of cascade system account for 88.85% and 41.46%, respectively. Besides, 66.35% of exogenous exergy destruction of middle heat exchanger is caused by the compressor and CO2 ejector, and to improve the performance of CO2 ejector and CO2 evaporator would decrease the exergy destruction of compressor. CO2 ejector and R290 ejector have the superior improvement potential in each subsystem compared to other components. The rise of ejector area ratio would increase the endogenous exergy destruction of ejector. For the system with high-performance compressor, R290 ejector efficiency should be attracted more attention to reduce its avoided endogenous exergy destruction.