Knowledge of the structural arrangement of the atoms in a solid is an important prerequisite to a detailed understanding of physical and chemical properties. In this work, structural investigations of phosphate (Ca-P-O) and aluminofluorophosphate (Na/Ba-Al-P-O-F) glasses with and without nitridation were performed. Nitrogen was introduced via metal nitrides (AlN, Ba₃N₂, or Ca₃N₂) or ammonia gas treatment of the melt. These glasses were characterized by chemical, thermal and optical techniques. Infrared, Raman, and MASS NMR spectroscopies were used to determine the local coordination and atomic structure of these glasses. The presence of peaks corresponding to P-O-P and PO₂ molecular vibrations in Ca-P-O glasses provided a basis for proposing a calcium metaphosphate glass structure comprised of long chains. As calcium oxide is added to calcium metaphosphate glasses, the long chains are broken up into shorter pyrophosphate units, as indicated by the presence of PO₃²⁻ terminal groups. MASS NMR of Ba-Al-P-O glasses showed that Al occurs as Al(4), Al(6), and either Al(5) or Al(6) linked through Al-O-Al bonds (such as in α-Al₂O₃). The addition of F in both the Ba-Al-P-O-F and Na-Al-P-O-F systems increases the relative abundance of Al(6). The ³¹P peak maxima in the MASS NMR spectra at about -5 to -10 ppm for Ba-Al-P-O-F-N glasses and -9 to -17 for Na-Al-P-O-F-N glass, indicate that pyrophosphate units dominate the structure of these glassy solids. Raman spectroscopy of a series of Al(PO₃)₃-NaF glasses showed that an increase in NaF content causes a shortening of the P-O-P chains and a more disrupted structural network. The presence of P-O-F units were observed only at the higher (>80 mole %) NaF contents. While the complexity of the Raman spectra make it difficult to confirm the presence of P-N bonding, glasses prepared in an ammonia atmosphere (nitrogen content of 1.6 wt%) suggest the possibility of P-N bonding on the basis of a vibrational peak at 826 cm⁻¹.