Biomass is known as a potential renewable energy source which can be used in the gasification process in order to produce biomethane gas. One of the major challenges encountered is the elimination of the high level of tar found in the syngas issued from the gasification process. The main purpose of this work is to conduct experimental measurements of liquid-liquid equilibria that will be used for tar removal from the biomass gasification process which is the important step before the distribution and the industrialization of the biomethane gas. In the present work, we propose an experimental and modeling study of liquid liquid equilibrium of ternary systems of water + solvent (methyl oleate) + model molecules of tar (benzene, toluene, phenol, thiophene, and pyridine) at 303.2 K, 323.2 K, and 343.2 K. The experimental results were correlated using the nonrandom two-liquid (NRTL) and UNIQUAC models and are used to feed the industrial needs for thermodynamic modeling.