Transient measurement techniques are applied for the kinetic investigation of the reaction mechanism of the carbon dioxide methanation, using diffuse reflectance infrared spectroscopy and mass spectrometry. The coupled information of the surface intermediates and the gas phase components time evolution leads to accurate identification of spectator species on the surface. Reaction intermediates, carbon monoxide and formates have been identified. The former is a key intermediate, and its hydrogenation leads to methane formation. The latter is fixed on the support, in equilibrium with a active formate species on the interface metal-support. A reaction mechanism is proposed including the formation step of the formates through a carbonate species.