Distillation is the most common methodology to ethanol purification but consumes a high amount of energy. In this work was evaluated a hybrid system using solvent liquid-liquid extraction (LLE) followed of conventional extractive distillation. The hybrid system was simulated using the software Aspen Plus® v.8.2. The solvent screening was based on ethanol distribution coefficient (KDE). N-octanol was selected as the better solvent to perform LLE. NRTL thermodynamic model was selected for achieving physical properties. From the sensitivity study, the highest ethanol recovery rate (>95%) was achieved with the solvent to feed ratio varying from 0.1 to 0.45. N-octanol was recovered in the first distillation column with 97% of purity. This proposed purification strategy obtained 38 L of anhydrous ethanol per hour which is quite similar to conventional process.