A novel approach to removing water from near-azeotropic ethanol water mixtures is proposed based on the hydration of ethylene oxide (EO) to produce ethylene glycol (EG) in a reactive distillation (RD) column. Steady-state simulations using the Aspen Plus software package were carried out to investigate the feasibility of the suggested approach, and a sensitivity analysis was carried out to obtain the optimal design parameters. The results showed that, using the optimal operating conditions, a reactive distillation column is capable of circumventing the azeotropic limitation to obtain anhydrous ethanol. Compared with traditional approaches, the proposed approach is promising because of its great potential for reducing energy consumption and capital costs.