The influence of near bandgap laser irradiation on the structure of the As50Se50 thin film has been investigated by synchrotron radiation photoelectron spectroscopy. The As 3d and Se 3d photoemission peaks of the irradiated sample show significant differences in shapes and positions in comparison with those obtained for non-irradiated amorphous film. The experimental data processing and quantifications are performed analyzing As 3d and Se 3d core-level components obtained by curve fitting. The relative contribution of the As and Se atoms in different chemical states to the whole As 3d and Se 3d signal, its structural origins as well as their relation to the As50Se50 nanolayers structure before and after laser irradiation is analyzed and discussed in detail. (C) 2012 Elsevier B.V. All rights reserved.