This work reports the phase-equilibrium measurements and thermodynamic modeling for the binary system CO2 + geraniol, and two ternary systems comprising these components and ethyl acetate or acetic acid, which are related to geraniol (trans)esterification using supercritical CO2 as a solvent. Measurements at each composition were carried out in a high-pressure variable-volume view cell at temperatures ranging from 303.2 to 343.2 K. The CO(2 )molar fraction ranged from 0.4120 to 0.9325 in the CO2 + geraniol system, from 0.5526 to 0.8000 in the CO2 + geraniol + acetic acid system, and from 0.6011 to 0.8993 in the CO2 + geraniol + ethyl acetate system. Under these conditions, vapor-liquid (VL), liquid-liquid (LL), and vapor-liquid-liquid (VLL) phase transitions were detected. The experimental data were modeled with the Peng-Robinson cubic equation of state with the van der Waals (vdW2) quadratic mixing rule.