Magnetron sputtered amorphous thin films a-WO3, a-MoO3 and doped a-WO3:Ir have been studied by X-ray absorption spectroscopy on the oxygen K-edge in comparison with crystalline oxides as monoclinic m-WO3, orthorhombic alpha -MoO3, cubic Na0.6WO3, layered-type hexagonal h-WO3 and WO3.H2O, having Variable electronic and atomic structure. The changes in the XANES ranging 10-15 eV above the absorption edge are interpreted based on the known band-structure calculations. The high-energy features are related to the multiple-scattering processes (EXAFS) at the nearest atoms.