Ce0.67Zr0.33O2 doped with iron oxide was prepared and the corresponding Pd-only three-way catalysts were examined and characterized. Pd/CZFe(1%) catalyst exhibits the best catalytic performance for CO, HC, NO and NO2 elimination and the widest operation window. The doping of iron oxide with 1% loading suggests the formation of more homogeneous Ce-Zr-Fe-O ternary solid solution, which seems to facilitate the reduction of Ce4(+) -> CO3+ or the formation of oxygen vacancy and to promote the interaction between Ce-Zr and Fe. Moreover, the Ce redox behaviour for surface reduction suggests depending not only on the formation of homogeneous Ce-Zr-Fe-O but also on the surface property of the sample. The increase in the concentration of oxygen vacancies under all atmospheres for CZFe(1%) sample also results in the enhancement of oxygen storage complete capacity. Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.