Chemical states of N-doped GeTe (N: 8.4 at.%) thin film (NGT) in structural phase transition were investigated by near-edge x-ray absorption of fine structure and high-resolution x-ray photoelectron spectroscopy with synchrotron radiation. We found the NaCl-like structure in NGT by x-ray diffraction at around 300 degrees C. Preparatory to the analysis of chemical states, after mild Ne(+) sputtering we obtained clean amorphous NGT, which showed the N(2) vibration mode peak in the N K-edge absorption spectrum. After annealing, the N(2) molecular peak disappeared completely and we assumed that nitrogen was contributed only to the Ge atom in structural phase transition by analyzing Ge 3d and Te 4d core-levels. (C) 2010 Elsevier B.V. All rights reserved.