Abstract: Process for purifying crude ethanol, whether produced by fermentation or by the synthetic route, to produce a pure ethanol-water azeotrope. The process uses only two distillation columns for fermentation ethanol and only three columns for synthetic ethanol because the latter has diethyl ether as impurity. The inventive concept lies in the design and specification of the columns and the specific distillation conditions which enable each of the impurities in ethanol to be reduced below 1 ppm. Ethanol of such purity is most desirable when used for potable or pharmaceutical purposes. The crude ethanol is fed into a first column and water is separately fed there as well, a side stream of purified aqueous ethanol is withdrawn from the first column and fed to a rectification column where a substantially pure ethanol-water azeotrope is withdrawn as a side stream. The points of introduction and removal of the respective streams to and from the columns are critical for a successful operation and product recovery.