The structure of Ni-C multilayer and single nickel layer samples has been analyzed before and after annealing, using two techniques: fluorescence EXAFS (F1EXAFS) at the Ni-K. edge and CuKα reflection. Annealing at a temperature of 450°C resulted in a change in the structure of the nickel layers from amorphous like to crystalline like. A reduction of the Bragg reflectivity by a factor of 7 was also found. Comparison between the EXAFS data of the annealed sample and of a nickel foil show a difference in the amplitude of the EXAFS. This is ascribed to a non-Gaussian atomic distribution of the backscattering atoms in the annealed sample around their average positions, whereas the atomic distribution in the (polycrystalline) Ni foil is a Gaussian one. From the annealing experiments we conclude that no irreversible changes take place in the structure of the nickel layers at temperatures below 200°C.