Structural characterisation of amorphous or partially amorphous thin films can be carried out by X-ray absorption spectroscopy in its X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) approaches. The EXAFS spectra have been analysed using the FEFF procedure, while XANES spectra are dealt with on a fingerprint basis. PbTiO3 and CoO/Co3O4 thin films prepared by ion beam induced chemical vapour deposition (IBICVD) have been chosen as case examples. For PbTiO3, comparison of X-ray diffraction (XRD) and XANES results show that the original film consists of a mixture of lead and amorphous TiO2. By annealing at 723 K, a well-crystallised PbTiO3 perovskite structure is formed without any segregation of titanium oxide or lead phases. As-prepared Cobalt oxides thin films were amorphous by XRD, but became crystalline by annealing at T greater than or equal to 573 K. Characterisation of the amorphous state in terms of the minimum size of clusters or homogeneity of the films was carried out by FEFF analysis of the EXAFS spectra. The combined used of the X-ray absorption spectroscopy (XAS) and XRD methods to structurally characterise thin films may provide information about the crystallisation processes that occur when amorphous thin films are annealed at high temperatures.