Solvent extraction method was studied using the methodology of preferable solvent selection and liquid-liquid equilibrium measurements. The method of solvent selection was based on the background of biofuel production. m-Xylene, the primary solvent, showed low distribution coefficient of ethanol and high separation selectivity of ethanol relative to water. A secondary solvent was employed to enhance the ethanol solubility, and capric acid, 1-hexanol and 2-ethyl hexanol were chosen from the carboxylic acids and higher alcohols. Addition of these secondary solvents enhanced the distribution coefficient but capric acid reduced the separation selectivity. The measured liquid-liquid equilibria were estimated with the ordinary and modified UNIFAC methods. Both methods could predict the liquid-liquid equilibrium behaviors of the measured systems, but the modified UNIFAC method could show a better correlation.