The Rh-ReO(x)/SiO(2) (Re/Rh = 0.5) exhibited high activity in the hydrogenolysis of ethers with an OH group. The C-O bond neighboring -CH(2)OH group was selectively dissociated: The hydrogenolysis of tetrahydro-5-methyl-2-furfuryl alcohol and 2-isopropoxyethannol gave 1,5-hexanediol and ethanol + isopropanol, respectively. This tendency suggests the regioselective C-O dissociation mechanism via anion intermediate formed by the attack of hydride and the subsequent protonation of the anion. (C) 2011 Elsevier Inc. All rights reserved.