A series of Ni catalysts were prepared with various supports (ZSM-5, Al2O3, SiO2, bentonite, TiO2, and kieselguhr) and their catalytic properties were investigated for the hydrogenation of cellobiose and glucose, the reaction intermediates of cellulose hydrolysis in hot-compressed water, in order to elucidate the key factors to control the hexitols selectivity in the hydrolytic hydrogenation of cellulose. For the hydrogenation of cellobiose, hexitols were produced with a selectivity above 82% over Ni/ZSM-5, but the other checked Ni catalysts produced large amount of glycerol, ethylene glycol, and propanediol, and the product distribution strikingly depended on the catalysts used. On the basis of kinetic experiments, it was the hydrogenation/dehydrogenation ability of Ni catalyst that played a critical role in controlling hexitols selectivity. High hydrogenation and inferior dehydrogenation activity of Ni catalysts were essential for obtaining high yield of hexitols in the hydrolytic hydrogenation of cellulose. The synergistic effect of Ni active species and acid-base sites was proposed to accelerate the dehydrogenation of sorbitol and thus reducing the yield of hexitols. (C) 2013 Elsevier Inc. All rights reserved.