Different contents of praseodymia were introduced to modify Ce(0.2)Zr(0.8)O(2) (CZ) and the supported Pd-only three-way catalysts before and after aging were also prepared. The influence of praseodymia doping on the structural/textural properties of CZ and the effect on the three-way catalytic activity were investigated. Structural and textural characterizations reveal that the addition of praseodymia results in the formation of Ce-Zr-Pr ternary solid solution (CZP) with higher specific surface area, better thermal stability and larger oxygen storage capacity (OSC) than that of CZ. It is more credible that Zr is replaced by Pr during the formation of CZP. The modified Pd-only three-way catalysts present relatively higher catalytic activity to the main target pollutants in gasoline engine exhaust and exhibit wider air/fuel operation window due to the improved properties of CZP. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.