The partial substitution of zirconium for praseodymium in a ceria-zirconia support was studied for WO3 or Nb2O5 supported catalysts dedicated to the NOx SCR by NH3. This partial substitution favored the support reducibility, but both niobium and tungsten impregnation strongly inhibited the redox behaviors of the support. Concomitantly, Nb2O5 and WO3 also provided acidic sites but praseodymium noticeably inhibited the ammonia storage, especially for WO3-containing sample. Finally, praseodymium drastically decreased the deNOx performances. Additional NO and NH3 oxidation experiments were performed and the various redox and acidic behaviors of all the studied materials were suitable to provide an overview of the reactional pathways which begins by the oxidative dehydrogenation of NH3 on acid sites. The generated species react either with oxygen species or with gaseous NO, reflecting a strong competition between the NOx SCR and NH3 oxidation together with the formation of a key intermediate in the nitrogen oxides reduction.