Although petroleum is widely used to make solvents and to produce energy, solvents derived from it, such as acetonitrile, may not be the safest and most sustainable options currently available. Additionally, processes such as the Fischer-Tropsch synthesis emerge as an intelligent alternative to produce energy from coal, biomass, or natural gas to supply the increasing demand for petroleum-derived products. Thus, with a green solvent, gamma-valerolactone, applied to the removal of oxygenated compounds from a Fischer-Tropsch process stream, this work suggests the application of a less toxic solvent to an alternative energy production process through model systems. In this sense, liquid-liquid equilibrium experimental data were measured for systems composed of an oxygenated solute (1-heptanol, propanone, 2-butanone, or 2-heptanone) + gamma-valerolactone + n-tetradecane at 298.15 K. The liquid-liquid equilibrium data were successfully correlated by the nonrandom two-liquid model with a medium average deviation lower than 1%. Therefore, the measured experimental data may contribute to the design of a liquid-liquid extraction process applied to the refinement of synthetic crude oil from a Fischer-Tropsch synthesis.