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The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and 31P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five- or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring-like germanate structures and P–O–Ge mixed linkages. The partial anionic N-for-O substitution gave rise to the linear dependence of the glass transition temperature (T g) and hardness (H V) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross-linking of the phosphate chains, but rather the short- and intermediate-range structural modifications within the germanate component of the oxynitride glasses.