Reduction of NO by CO catalysed by Rh/CeO2-ZrO2 solid solutions is investigated with the aim to elucidate the role of the CeO2-ZrO2 supports in modifying the activity of supported Rh. Two distinct kinetic regimes, characterised by different activation energies are observed below and above 500 K. It is proposed that below 500 K the reduction of NO occurs at the expenses of a concomitant oxidation of Ce3+ sites. In this model, the supported metal activates the reducing agent favouring the efficiency of Ce4+/Ce3+ redox couple. The influence of a high temperature reduction (H-2, 1073 K) is also investigated. Such a treatment, which increases the reducibility at low temperatures of the CeO2-ZrO2 solid solution, promotes the efficiency of the catalysts at low temperatures, confirming the important role of the Ce4+/Ce3+ redox couple in determining the activity of the catalyst.