The adsorption and decomposition of ethylene glycol on Rh(100) have been studied with temperature-programmed reaction spectroscopy and reflection absorption infrared spectroscopy. Ethylene glycol adsorbs onto the surface via the hydroxyl groups. At 150 K, both hydroxyl bonds are broken, forming an ethylenedioxy intermediate. At high coverage, a portion of the ethylene glycol molecules dehydrogenate only one hydroxyl bond, forming a monodentate species. These intermediates decompose further, with complete dehydrogenation and simultaneous CC bond breaking occurring at around 290 K. Hydrogen and carbon monoxide are formed, which desorb at 290 and 500 K, respectively.