Modification of Rh/C with Re species enabled chemoselective hydrogenolysis of tetrahydropyran-2-methanol to 1,6-hexanediol. In particular, the Rh–ReOx/C (Re/Rh ratio=0.25) catalyst gave a high yield of 1,6-hexanediol (84 %) and showed a very low activity for overhydrogenolysis to 1-hexanol. Using the same catalyst in the hydrogenolysis of tetrahydrofurfuryl alcohol also gave a high yield of 1,5-pentanediol (94 %). Characterization results indicate the formation of ReOxclusters attached on the surface of Rh metal particles. This can cause the synergy between ReOxand Rh, and the tetrahydropyran-2-methanol hydrogenolysis proceeds on the interface between Rh metal surface and attached ReOxspecies.