Standard EXAFS analysis on CexZr1-xO2 mixed oxides leads to incorrect structural parameters. A comparison of XRD Rietveld analysis with an EXAFS study of a Y-doped reference compound and a Ce0.5Zr0.5O2 catalyst showed that in order to obtain reliable structural parameters with EXAFS an anharmonic pair distribution function has to be used for the analysis of the second Zr-O bond. The anharmonicity of the second Zr-O subshell points to a much weaker Zr-O bond than in the first Zr-O subshell. A lamellar type structural model explains the high oxygen storage capacity of Ce0.5Zr0.5O2. The short Zr-O-1 distance corresponds to the intralayer Zr-O bond and the much weaker Zr-O-2 distance to the interlayer Zr-O interaction. The oxygen storage capacity is determined by the interlayer Zr-O interaction.