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• RhCl 3 was supported on CeO 2 by Deposition–Precipitation (DP) and Impregnation (Imp) methods. • The catalysts prepared were tested in propylene and carbon black total oxidation. • In DP: EPR evidenced O 2 − presence and XRD detected Rh 2 O 3. • DP is more active than Imp due to Rh 2 O 3 , O 2 −, as well as to easier reducibility and lower particle size of rhodium species. 4 wt% Rh/CeO 2 catalysts were prepared by two different methods: deposition–precipitation (DP) and impregnation (Imp). X-ray diffraction (XRD), differential scanning calorimetry and thermogravimetry (DSC-TG), temperature-programmed reduction (TPR), and electron paramagnetic resonance (EPR) were used for physicochemical characterization. The solids were tested in propylene and carbon black oxidation reactions. The 4%Rh/CeO 2 (DP) showed better catalytic performance in both reactions compared to the catalyst prepared by the impregnation method. The XRD technique evidenced the formation of Rh 2 O 3 phase in the DP-solid after calcination of this latter at 400 °C for 4 h. EPR evidenced, only in the DP-solid, the presence of O 2 − species in interaction with the CeO 2 surface whereas Rh4+ ions in the form of clusters were identified in both solids. The TPR technique showed that the DP-solid was reduced by hydrogen at lower temperature compared to the impregnated one. The higher catalytic performance of the DP-solid was attributed to the presence of O 2 − species along with the presence of Rh 2 O 3 phase in ceria and to the better reducibility and lower particle size of the rhodium species. [ABSTRACT FROM AUTHOR]