Zr-L 2, 3 XANESs of tetravalent zirconium oxides with different coordination numbers and local symmetries are systematically investigated by ab initio multiplet calculations using fully relativistic molecular spinors for model clusters. Experimental Zr-L 2, 3 XANESs are obtained for SrZrO 3, m-ZrO 2 (monoclinic) and t-ZrO 2 (tetragonal). The theoretical spectra are in good agreement with the experimental data. The multiplet effects are found to play essential roles in determining the peak shape. The shapes of L 3-and L 2-edges are systematically different. The intensity ratios of the doublet peaks at both L 3-and L 2-edges are found to be sensitive to the coordination number of Zr. The ratio can therefore be used to estimate the coordination number of Zr in such oxides.