This study presents the analysis of the exergy load distribution in a separation process by extractive distillation for ethanol dehydration. The methodology carried out is divided into three parts: the calculation of the flow exergy considering the physical and chemical exergies of the distillation process; the calculation of the primary and transformed exergy contributions considering the consumed exergy; and finally, the overall process efficiency, which shows the real percentage of energy being used in the process. The simulation of an extractive distillation separation system is carried out using Aspen Plus^®, from Aspen Tech Version 9. In general, heat transfer processes (heating or cooling) are the ones that generate the greatest exegetic destruction, which is why they must be the operations that must be optimized. As a result of our case study, the local exergy efficiency of the extractive distillation column is 13.80%, which is the operation with the greatest energy loss, and the overall exergy efficiency of the separation system is 30.67%. Then, in order to increase exergy efficiency, a sensitivity analysis is performed with the variation of the azeotrope feed, number of stages, reflux ratio, and solvent feed variation on ethanol purity to reach an overall efficiency of 33.53%. The purity of ethanol is classified as higher than that of the specified, 99.65%.