PURPOSE:To obtain ethanol in high efficiency and inexpensively by effectively using sources, by saccharifying and fermenting a polysaccharide as a raw material, separating selectively and concentration alcohols from an unrefined fermented matter by the use of a water repellent membrane, recovering remaining enzyme and saccharide and reusing them. CONSTITUTION:A polysaccharide such as starch, cellulose, etc., is used as a raw material, it is saccharified in the presence of a decomposition enzyme, to the saccharified solution is added yeast essence and the solution is fermented. The, the unrefined fermented matter is heated to 30-50 deg.C, passed through a water-repellent porous membrane 1 by the use of a principle of thermo.vaporation, only volatile substances such as ethanol, etc., are passed through and transferred to a permeated solution side at 10-20 deg.C, selectively separated and concentrated and the remaining enzyme and saccharide are recovered, circulated through saccharification and fermentation processes and reused, to efficiently obtain ethanol.