Hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol and other related substrates such as 3-hydroxytetrahydrofuran and 1,2-cyclohexanediol proceeds over Ir-ReOx/SiO2 catalyst. TOF values are higher than those of Rh-ReOx/SiO2, which has been reported to be an effective catalyst. The selectivity to the product, where the C-O bond neighboring the C-OH group in the substrate is dissociated, is comparable to or higher than that of Rh-ReOx/SiO2. Hydrogenolysis of most substrates except 1,2-cyclohexanediol proceeds via the direct mechanism where hydride species formed from hydrogen molecule attacks the anti-position of C-O bond. In the case of hydrogenolysis of 1,2-cyclohexanediol where attack of anti-position of C-O bond is unfavorable, indirect mechanism involving dehydrogenation to 2-hydroxycyclohexanone is responsible for the formation of cyclohexanol. (C) 2012 Elsevier Inc. All rights reserved.