The effect of Pt addition on the performance of Ni/CeO2 catalyst for the low temperature steam reforming of ethanol is investigated. The reaction mechanism was explored using diffuse reflectance infrared spectroscopy under reaction conditions and temperature-programmed surface reaction of ethanol. The addition of Pt to Ni/CeO2 catalyst promoted the decomposition of dehydrogenated and acetate species to hydrogen, methane, CO and carbonate species. Furthermore, the presence of Pt reduced the rate of catalyst deactivation. In situ X-ray absorption studies revealed the formation of a nickel carbide phase during steam reforming of ethanol over Ni/CeO2 catalyst, which was associated with amorphous carbon deposition and catalyst deactivation. X-ray photoelectron spectroscopy in combination with kinetic and structural data was consistent with a partial Pt monolayer on Ni in the bimetallic catalyst. The segregation of Pt on the surface of the Ni particles minimized the formation of nickel carbide and promoted catalyst stability. (C) 2015 Elsevier B.V. All rights reserved.