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The new configuration of a transcritical CO2 ejector expansion refrigeration cycle combined with a dedicated mechanical subcooling cycle (EMS) is proposed. Three mass ratios of R32/R1234ze(Z) (0.4/0.6, 0.6/0.4, and 0.8/0.2) were selected as the refrigerants of the mechanical subcooling cycle (MS) to further explore the possibility of improving the EMS cycle's performance. The thermodynamic performances of the new cycle were evaluated using energetic and exergetic methods and compared with those of the transcritical CO2 ejector expansion cycle integrated with a thermoelectric subcooling system (ETS). The results showed that the proposed cycle presents significant advantages over the ETS cycle in terms of the ejector performance and the system energetic and exergetic performances. Taking the EMS cycle using R32/R1234ze(Z) (0.6/0.4) as the MS refrigerant as an example, the improvements in the coefficient of performance and system exergy efficiency were able to reach up to 10.27% and 15.56%, respectively, at an environmental temperature of 35 °C and evaporation temperature of −5 °C. Additionally, the advantages of the EMS cycle were more pronounced at higher environmental temperatures. [ABSTRACT FROM AUTHOR]