AbstractThe hydrogenolysis of erythritol using an Ir–ReOx/SiO2 catalyst was performed for the production of butanediols, which are widely used as a raw material of polymers. The activity and selectivity to butanediols on Ir–ReOx/SiO2 was much higher than that on conventional hydrogenolysis catalysts. The maximum selectivity to 1,4‐ and 1,3‐butanediols reached 33 and 12 % at 74 % conversion, respectively. The erythritol conversion and selectivity to butanediols was almost maintained during four repeating tests if small amounts of acid were added to the reaction and the catalyst was calcined again. The reaction kinetics, reactivity trends, and characterization results indicate a direct hydrogenolysis mechanism in which the hydride species on the Ir metal surface attacks the alkoxide species on the 3D ReOx clusters. Based on the production of erythritol by the fermentation of glucose and glycerol, erythritol hydrogenolysis may be a promising pathway for the production of biobutanediols.