A cellulose derivative membrane (30 wt.% cellulose acetate butyrate (CAB) combined with 70 wt.% cellulose acetate propionate (CAP)) was prepared, and its properties were evaluated by the pervaporation separation of mixtures of ethyl tert-butyl ether (ETBE) and ethanol. The experimental results showed that the selectivity and permeability of the membrane were dependent on the blend composition, the processed feed and the experimental temperature. With respect to the temperature, the fluxes obeyed the Arrhenius equation. On the basis of these results, a separation process for the production of ETBE was developed by combining pervaporation and distillation. The distillation column was designed with the software ASPEN PLUS, and the liquid-vapour equilibria were predicted by the UNIFAC method. The area of the membrane was calculated according to the production capacity. It may be concluded that the combined process for the separation of mixtures of ETBE and ethanol is simple with high recovery of the ETBE product.