Abstract Carbon dioxide hydrogenation has been performed on Rh/TiO 2 and Rh/Nb 2O 5 catalysts and the effects of metal reduction conditions have been investigated. C 1–C 6 hydrocarbons have been detected and shown to follow Anderson-Schulz-Flory (ASF) statistics. In the case of Rh/TiO 2 the role of carbon monoxide as an intermediate in carbon dioxide hydrogenation has been clearly evidenced. In both catalysts the formation of the SMSI state (strong metal-support interactions) during high-temperature reduction strongly influenced catalytic activities and selectivities. On Rh/Nb 2O 5 the SMSI state was found to be labile in catalytic conditions whereas on Rh/TiO 2 it was maintained because of the presence of hydrogen which slowed down the oxidation process operated by water.