As the most promising biomass utilization method, biomass gasification is gaining attention as a route for biomass energy production, but the syngas generated from the process contains unacceptable levels of tar. The syngas in reality leads to a liquid-liquid-vapor equilibrium. This syngas becomes saturated with water steam, solvent, and trace of volatile tar. The aim of this work is to study the liquid-(liquid)-vapor equilibrium of extracting solvents (P-xylene, methyl hexadecanoate, and methyl oleate), binary systems (water + solvents), and ternary systems (water + methyl hexadecanoate + model molecule of tar) and to determine the vapor pressure for those systems from 303.15 to 453.15 K. Vaporization enthalpies of each solvent at 298.15 K are also calculated and compared to the literature. The obtained data were correlated using the nonrandom two-liquid (NRTL) model for the liquid phase combined with the perfect gas equation for the vapor phase.