Lithium phosphorus oxynitride (LiPON) is a solid state electrolyte commonly used in thin film batteries (TFBs). Advanced TFBs face the issue of detrimental electrode-electrolyte interlayer formation, related to the electronic structure of the interface. In this contribution, we study the valence band structure of LiPON using resonant photoemission and synchrotron photoemission with variable excitation energies. The identification of different valence band features is done according to the known valence band features of meta- and orthophosphates. Additionally we compare our results with partial density of states simulations from literature. We find that the valence band structure is similar to the known metaphosphates with an additional contribution of nitrogen states at the top of the valence band. From the results we conclude that synchrotron X-ray photoemission (XPS) is a useful tool to study the valence band structure of nitridated alkali phosphate glasses. (C) 2014 Elsevier B.V. All rights reserved.