Abstract: CO₂+HFC binary mixtures have good performance and environmental friendliness and are considered good alternative working fluids in cooling and power cycle systems. The vapor-liquid phase equilibrium properties are key to the calculation of the enthalpy and entropy of mixtures, which is critical for the analysis of cooling and power cycle systems. To accurately predict the vapor-liquid equilibrium of CO₂ and HFC (R23, R32, R41, R125, R134a, R143a, R152a, R161, and R227ea) binary mixtures, a group contribution model based on the excess free energy (G^E) mixing rules (PR+MHV1+UNIFAC and PR+LCVM+UNIFAC) is established in this paper. The interaction parameters between groups such as -CO₂, -Alkane, -CHF, and -CHF₃ are obtained by the vapor-liquid phase equilibrium experiment of CO₂ and HFC refrigerants, and these group parameters are critical for predicting their vapor-liquid phase equilibrium properties (the pressures and vapor phase molar fractions). The AARDp value calculated by the PR+LCVM+UNIFAC model is 5.53%, the value of AADy₁ is 0.0132, and the AARDp and AADy₁ values of the PR+MHV1+UNIFAC model are 7.40% and 0.0229, respectively. However, for the CO₂+R32 system, the PR+MHV+UNIFAC prediction model can reproduce the experimental data with lower deviations, and the values of AARDp and AADy₁ are 1.53% and 0.0045, respectively. In summary, for CO₂+HFC binary mixtures, the PR+LCVM+UNIFAC group contribution model can reproduce the experimental data with lower deviations, but for individual CO₂ binary mixtures (such as CO₂+R32), the PR+MHV1+UNIFAC model also has unique advantages. According to the prediction results of the group contribution model, the PR+LCVM+UNIFAC model has significantly improved the calculation progress compared with the PR+MHV1+UNIFAC model used in the previous system.