Isothermal (P-x-y) vapor–liquid equilibrium data for the CO2 + 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) binary system are reported at seven temperatures ranging from 283.15 K to 353.15 K. The experimental values were measured using a static–analytic type apparatus coupled with two electromagnetic capillary samplers (Rolsi™, Armines' patent) for repeatable and reliable equilibrium phase sampling and handling. Moreover, for the four temperatures above the critical temperature of pure CO2 (304.3 K), the mixture critical compositions (xc) and pressures (Pc) were calculated at each temperature using extended scaling laws. In a second step, the critical loci of the CO2 + R1234yf and CO2 + trans-1,3,3,3-tetrafluoroprop-1-ene [R1234ze(E)] were measured over the whole composition range using a synthetic-dynamic type apparatus. The subcritical and critical experimental data determined in this study were compared to those available in the open literature and were correlated using the Peng–Robinson equation of state with temperature-dependent binary interaction parameters.