This work reports phase equilibrium measurements for the binary {CO2(1) + ethyl palmitate(2)} and ternary {CO2(1) + ethyl palmitate(2) + ethanol(3)} systems at high pressures. There is currently great interest in biodiesel production processes involving supercritical and/or pressurized solvents, such as non-catalytic supercritical biodiesel production and enzyme-catalysed biodiesel production. Also, supercritical CO2 can offer an interesting alternative for glycerol separation in the biodiesel purification step in a water-free process. In this context, the main goal of this work was to investigate the phase behaviour of binary and ternary systems involving CO2, a pure constituent of biodiesel ethyl palmitate and ethanol. Experiments were carried out in a high-pressure variable-volume view cell with operating temperatures ranging from (303.15 to 353.15) K and pressures up to 21 MPa. The CO2 mole fraction ranged from 0.5033 to 0.9913 for the binary {CO2(1) + ethyl palmitate(2)} system and from 0.4436 to 0.9712 for ternary system {CO2(1) + ethyl palmitate(2) + ethanol(3)} system with ethyl ester to ethanol molar ratios of (1: 6), (1: 3), and (1: 1). For the systems investigated, vapour-liquid (VL), liquid-liquid (LL) and vapour-liquid-liquid (VLL) phase transitions were observed. The experimental data sets were successfully modeled using the Peng-Robinson equation of state with the classical van der Waals quadratic (PR-vdW2) and Wong-Sandler (PR-WS) mixing rules. The PR-WS showed good performance in the prediction of the phase transition for the ternary systems based on the binary system data. (C) 2012 Elsevier Ltd. All rights reserved.