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X‐ray absorption fine structure (XAFS) above the Fe K‐edge and the Ce L3‐edge in amorphous Al90FexCe10‐x (x = 3, 5, and 7) alloys have been measured and analyzed. Quantitative analyses of the Fe K‐edge and Ce L3‐edge EXAFS spectra are limited to local structure parameters of the first coordination sphere. Using a theoretical multiple scattering (MS) approach, we show that the Fe and Ce XANES are sensitive to the structure of coordination spheres, which extend up to nearly 4.5 Å. Comparison of experimental XANES spectra with theoretical MS results allows one to determine the local structure around the iron and cerium sites up to at least the third shell of atoms.