Valeric biofuels are renewable and environmental friendly fuels whose production avoids the competition with the food industry for edible oils since its route of production uses lignocellulose of residue from crops as raw material. After the reaction steps several purification operations are necessary for the valeric biofuels to meet purity standards. Therefore, it is of utter importance the knowledge of both liquid-liquid (LLE) and vapor-liquid (VLE) equilibrium behavior of species present in the process, such as ethyl valerate, valeric acid, ethanol and water. In this sense, the objective of this work is to provide a general overview for the phase equilibria of the system aforementioned using experimental data collected as background for the thermodynamic modeling. Experimental data concerning to LLE were evaluated at local atmospheric pressure (around 90.9 kPa) and 293.15 K and 318.15 K, while VLE data were collected at several different controlled pressures, ranging from approximately 7 kPa to local atmospheric pressure (around 91 kPa). UNIFAC and PC-SAFT (Perturbed Chain form of the Statistical Associating Fluid Theory) were used to perform the thermodynamic modeling. The results obtained in this work are helpful to prove the importance of carefully evaluate the interactions between the molecules present in the system. Otherwise, the design of unit operations could underestimate the number of stages required for the purification, causing the products to not reach purity specifications. (C) 2018 Elsevier B.V. All rights reserved.