The decrease in the oil supply and increasing environmental concerns boost the demand for alternative biofuels. In this context, biobutanol production from acetone-butanol-ethanol (ABE) fermentation comes forward as a remarkable process alternative. The main drawback of this alternative is the production of dilute fermentation broth which results in very energy demanding separation steps. Thus, several hybrid separation techniques have been studied combining extraction and distillation technologies to develop energy efficient separation processes. However, these techniques bring their own disadvantages, while they are solving the well-known drawbacks. In this study, a novel process including reactive distillation columns is proposed to purify biobutanol from acetone-butanol-ethanol (ABE) fermentation. The results indicate that there is a significant decrease in the reboiler heat duties. In addition, a co-product (ethylene glycol) is obtained as the result of the reaction taking place in the process besides the purification of butanol, ethanol and acetone.