We have studied the effect of the film thickness on the electronic structure of pure nickel and iron thin films. Series of the thin films were evaporated by e-beam evaporation on SiN substrates. The electronic structure of the thin films was investigated using X-ray absorption near edge structure (XANES) spectroscopy. We have showed the thickness dependent variation of the experimental branching ratio (BR) and full-width at half-maximum (FWHM) at the L 3 and L 2 edges for both thin films. A strong thickness dependence of the L 2,3 BR and FWHM was found. We have also focused on the deviation of L 3 to L 2 ratio from its statistical value. The average L 3 /L 2 white-line intensity ratio was calculated to be 3.4 and 3.0 from peak height and integrated area under each L 3 and L 2 peaks, respectively for iron. Additionally, a theoretical L 2,3 edge calculation for nickel was presented. The obtained results were consistent with the general view of the L 2,3 BR and FWHM of iron and nickel transition metals.