The application of transcritical CO2 cycle in the thermal management system of electric vehicles has become increasingly prevalent, but the existing thermal management system architecture has not been optimized to specifically enhance the performance of CO2 refrigerant. This paper analyzes the impact of various heat exchanger arrangements on CO2 thermal management system and evaluates system configurations based on a new performance index, cycle coefficient of performance. The effects of air temperature, ambient temperature, and heat load on system performance are conducted with a high precision model. The chiller is connected in parallel-series with indoor heat exchangers, resulting in a maximum coefficient of performance improvement of 27.89% at an indoor air inlet temperature of 10 °C, and a maximum coefficient of performance improvement of 21.69% at an ambient temperature of 5 °C, under simultaneous heating conditions. The radiator is placed on the windward of gas cooler, leading to a maximum coefficient of performance increase of 4.85% in heating mode, but a maximum coefficient of performance decrease of 9.84% in cooling mode. The evaluation of these configurations across different operating cycles reveals that the parallel-series connection is well-suited for the new European driving cycle, showing an 18.4% improvement in cycle coefficient of performance compared to the series-parallel connection. The windward arrangement of radiator proves effective for highway fuel economy test cycle in winter and the new European driving cycle in summer. This study provides effective instruction for configuration design and evaluation of transcritical CO2 vehicle thermal management systems.