Nickel oxide is a p‐type semiconductor with wide band gaps of 3–4 eV. The defects of O or Ni atoms are essential to explain some specific features of the semiconductors. The information of the local structure around Ni is important to clarify the conduction mechanism. We investigate the Ni K‐edge X‐ray absorption fine structure spectra of the nickel oxide thin films in order to obtain the structural information around Ni. For the X‐ray absorption near edge structure (XANES) analyses, we apply a full multiple scattering theory. The experimental results suggest that the crystallinity of the thin films depends on the annealing temperature. The distances of Ni–O and Ni–Ni are 1.984 and 2.747 Å for the sample annealed at 100 °C and 2.084 and 2.947 Å for the sample annealed at 300 °C, respectively. Our multiple scattering calculations can satisfactorily explain the experimental result. Copyright © 2014 John Wiley & Sons, Ltd.