Fossil sources of energy become focus of many debates due to the pollution caused by them. In this scenario, renewable fuels, as biodiesel, are studied to improve their production efficiency and become more competitive with fossil fuels and even substitute them. Biodiesel, produced by the transesterification reaction, is constituted by a mixture of fatty acid esters and needs to be separated from its reactional solution in order to be commercialized. To improve the separation processes, the thermodynamic behavior of the mixtures involving components of the biodiesel needs to be known. Aiming this, the vapor–liquid equilibrium (VLE) of the methanol + methyl palmitate and ethanol + ethyl palmitate systems was analyzed at 50.3 and 101.3 kPa and the experimental data were submitted to a thermodynamic consistency test and thermodynamic modeling with the Peng-Robinson (PR), Group Contribution Volume Translated Peng-Robinson (GC-VT-PR) and the Perturbed Chain - Statistical Associating Fluid Theory (PC-SAFT) equations of state. Experimental data were considered thermodynamically consistent, and the modeling showed good results in terms of the lowest relative deviations of temperature and vapor mole fraction obtained with the GC-VT-PR and PC-SAFT models.