The glass based on a 1.5SiO2-Al2O3-0.5P2O5-CaO-0.67CaF2 composition was produced and substituted gradually by barium. The structure of the glasses was studied by multinuclear Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR) and Fourier Transform Infrared Spectroscopy (FTIR). It was indicated by 29Si and 31P MAS-NMR spectra that silicon was present as Q4 (4Al) and Q3 (3Al) species and phosphorus was in a Q1 pyrophosphate environment. 29Al MAS-NMR spectra showed that four fold coordinated aluminum Al (IV) was the dominant species with a second peak assigned to octahedral aluminum Al (VI). The 19F spectra suggested that the barium addition caused the formation of Al-F-Ba(n) and F-Ba(n) species. Furthermore, a distribution of silicate network including Si-O-Si stretching (Q4 and Q3) and Si-O-[NBO] (Q3) per SiO4 was reflected by the FTIR study.