The effect of ruthenium on the physico-chemical properties of CeZr and CeZrCo mixed oxides for H-2 production by glycerol steam reforming reaction has been studied. The combination of in situ Raman spectroscopy under both reductive and oxidative conditions, H-2/O-2 pulses and XRD, Raman, BET analysis, H-2-TPR and TPD-TPO analyses contributed to the determination of the structural and textural properties, redox behavior, re-oxidation capacity and resistance to carbon deposition of the synthesized catalysts. The results show that the catalytic activity is improved by the (positive) cooperative and complementary effect between cobalt and ruthenium that favors the selectivity toward the steam reforming, selective to H-2, with respect to the unselective thermal decomposition of glycerol. Ruthenium stabilizes the cobalt cations inserted in the fluorite structure preventing its rejection as Co3O4; and provides the necessary hydrogen to reduce Ce4+. The combination cobalt-ruthenium modifies positively the redox properties of the catalysts, increases the re-oxidation capacity (OSC) and promotes the gasification of the carbon deposits. Under the reaction conditions, the decrease in glycerol conversion came along with a change of selectivity. The formation of H-2 and CO2 were strongly decreased, while the formation of CO, C2H4 and condensable products (mainly hydroxyacetone) increase. The differences in the catalytic stability and activity of the catalysts are related to the capability of the catalysts to activate H2O under the reaction conditions, favoring the steam reforming reaction over the thermal decomposition. (C) 2014 Elsevier B.V. All rights reserved.