Cu L₃-edge XANES spectra of Cu-aluminate catalysts were recorded to clarify the local structure of Cu²⁺ cation in alumina matrix. XANES spectra of Cu-aluminate exhibited two different peaks, which were assigned, by comparison with those of reference compounds, to Cu²⁺ in tetrahedral and octahedral sites. To estimate the fraction of these Cu²⁺ species, a deconvolution analysis of XANES spectra was carried out. For CuAl₂O₄ (stoichiometric spinel), the ratio of the peak areas of the deconvoluted spectrum was in good agreement with the ratio of tetrahedral/octahedral previously determined by X-ray diffraction method. Thus, it is concluded that the fraction of Cu²⁺ ions on tetrahedral and octahedral sites can be estimated quantitatively from Cu L₃-edge absorption spectra. This method was applied to a series of copper-aluminate catalysts, and it was shown that the fraction of Cu²⁺ on tetrahedral sites increased as Cu content increased.