The redox properties of ceria were investigated by temperature-programmed reduction performed under hydrogen and the catalysts were evaluated by determining the temperatures at which 50% conversion for propene and propane oxidation were reached, The results obtained show that ceria plays a decisive role within the preparation of bimetallic Pt-Rh/Al2O3-CeO2 catalysts by successive impregnations (SI) when reduced capping cerium atoms (Ce3+) are present on the parent Pt/Al2O3CeO2 catalyst before introduction of the rhodium salt. Thus, rhodium deposition would occur by a redox reaction between Ce3+ and Rh3+. The preparation procedure of Pt-Rh/Al2O3-CeO2 catalysts by the SI method increases the thermal stability of the metallic species under oxidizing conditions. This improvement would be the consequence of a higher resistance to the formation of Pt-Rh alloys with surface enrichment in rhodium.