Adsorption with starchy and cellulosic materials was evaluated as an energy efficient technology for ethanol dehydration. Corn (Zea mays), upright elephant ear (Alocasia macrorrhiza), cassava (Manihot esculenta), and sugar cane bagasse (Saccharum), were used as sources of starch and cellulosic fibers and further used as adsorbents for water removal, Enzymes (alpha-amylase and cellulase for starch and Cellulose, respectively) were evaluated as modifying agents with the aim of increasing water adsorption capacity. Native and enzyme-treated materials were examined with SEM, XRD, and BET analysis to determine the hydrolysis influence on structure and superficial area, Partial hydrolysis was obtained under operation conditions evaluated, as was shown by the SEM micrographs. Crystallinity increased with the enzymatic hydrolysis for all materials. For all materials, superficial area was not increased with enzymatic hydrolysis but water adsorption capacity was improved reaching an anhydrous product with enzyme-treated materials. Water adsorption capacity ranges from 4 to 19 g/ 100 g adsorbent were found for evaluated materials. Corn starch had the highest water adsorption capacity (19 g/ 100 g ads) while upright elephant car starch presented the lowest (4.2 g/ 100 g ads). Tested materials showed affinity with water for both native and enzyme-treated cases. This allowed water to adsorb from the feed for obtaining anhydrous ethanol. It was suggested that water adsorption capacity was increased because of the more exposed hydroxyl groups from the polymeric structures evaluated (starch and cellulose). Applicability of these materials was oriented to small scale ethanol production plants in developing countries where rural areas are the objective and small productions are expected.