The local aluminum structure in zeolite mordenite was studied at temperatures up to 1000 K in a vacuum by Al K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The interatomic aluminum-oxygen distances and the number of coordinating oxygen atoms were determined by Fourier transform analyses of experimental Al K-edge XANES spectra and the fits of the nearest oxygen atoms contributions, using a limited number of variables. The values of fixed parameters for Fourier transform and fit are established from the spectrum of Na-mordenite, considered the reference compound for the studied zeolites H-mordenites, which was also used to test the accuracy and the stability of the determined structural parameters. To reveal the aluminum coordination in H-mordenite at various temperatures, the Fourier transform peak of the coordinating oxygen polyhedron was fitted first with a single-shell model, and the obtained structural information was refined by the fits, on the basis of the most plausible models for the aluminum coordination environment. The choice of such models for each temperature was performed according to the qualitative predictions on the aluminum local atomic structure provided by the preedge data analysis and 27 Al magic angle spinning (MAS) NMR experiments. By this method, the presence of sixfold aluminum atoms, aside from the fourfold ones, in H-mordenite at room temperature was revealed quantitatively, and the concentrations of these mixed coordinations were determined; the structural distortion of the oxygen tetrahedron around aluminum in dehydrated H-mordenite at T = 575 K was found to be strong, and the corresponding Al-O distances for this distortion were obtained; for H-mordenite at 985 K, the presence of threefold coordinated aluminum atoms, aside from the fourfold ones, was revealed, and an estimate of the amount of threefold aluminum was given.