The hydrogenolysis of methyl α-D-glucopyranoside at elevated temperatures and pressures with copper chromite as catalyst and anhydrous dioxane as solvent was studied. The reaction produced a complex mixture of alcohols, the major components being 2-hydroxymethyl-4,5-dihydroxytetrahydropyran, methanol, isomeric hexanediols, 1,2-propanediol, and ethanediol.