Alumina-supported zirconia catalysts, containing from 2.1 to 20.1 wt% ZrO2 and prepared by multiple incipient wetness impregnation using benzene solutions of zirconium acetylacetonate, were characterised using the EXAFS technique. The results indicated that the supported phase consists of Zr4+ species that do not have Zr as second neighbours, hexacoordinated to oxide anions, suggesting that these ions occupy octahedral positions in the defective spinel structure of the γ-alumina support. In order to test this hypothesis, an idealised unit cell was constructed with the formula ZrAl4O8, with spinel structure. Atomic positions in this cell were optimised using theoretical calculations based on DFT. The smallest energies corresponded to structures where the Zr4+ ions occupy octahedral sites in the spinel structure. Simulations of the EXAFS spectra using this structure provided excellent agreement between the theoretical and experimental spectra.