A new azeotropic distillation process is presented to produce gasohol in an adequate concentration of bioethanol and isooctane, which emulates the properties of gasoline ready to use in conventional combustion engines. Since the mixing step is eliminated, there are significant economic savings which imply a competitive price of bioethanol. A comparison is provided with the traditional bioethanol dehydration process, extractive distillation. Both processes were simultaneously designed and optimized with differential evolution with a Tabu list algorithm (DETL) in order to reduce the total annual cost (TAC). Results showed that when obtaining E10 biofuel, a blend of up to 10% ethanol and 90% unleaded isooctane, via azeotropic distillation, over 40% of the TAC is saved compared to obtaining pure alcohol dehydrating through extractive distillation. Moreover, the reduction in carbon dioxide emissions results in an average of 27%.