Bioethanol is among the most promising of biofuels because it has an energy content similar to gasoline while generating lower pollutant emissions than gasoline. But, in order to be used as an automotive fuel mixed with gasoline, ethanol must have less than 0.5 wt % of water. To achieve required ethanol purity, in light of the fact that the ethanol-water mixture forms an azeotrope, unconventional separation techniques such as extractive distillation or azeotropic distillation are necessary. However, the purification of ethanol using conventional distillation followed by extractive distillation has the disadvantage of high cost of services. Thus, this study proposes alternative hybrid systems using liquid-liquid extraction and extractive distillation. The use of n-dodecane as entrainer for liquid-liquid extraction and glycerol as entrainer for extractive distillation has been considered. The proposed systems are analyzed and a comparison is done on their performance in terms of energy and total annual cost. It has been found that the hybrid scheme presents both lower total energy consumption and lower total annual cost as compared to the traditional purification scheme with conventional distillation and extractive distillation.