This paper presents the results of a study of the thermal properties, X-ray powder diffraction (XRPD), NMR and solubility of a range of phosphate-based glasses. Ion release and pH measurements were also obtained. The compositions were limited by fixing the P2O5 mol% content at 45, 50 and 55 mol%, and varying the CaO mol% at 30, 35 and 40 mol%. Initial data collected from thermal analysis showed an increase in the Tg values, with increasing CaO mol%, as expected. An increase in crystallisation temperatures with increasing CaO mol% was also observed, with sharp peaks indicating the presence of single and/or double phases. Initial XRPD data revealed that the 45 mol% P2O5 precipitated a calcium bridged trimetaphosphate (Na4Ca[PO3]6) at the sodium oxide contents of 25 and 20 mol%, but at the 15 mol% level two phases formed, NaCa[PO3]3 and Ca2P2O7. The 50 mol% P2O5 compositions showed two sodium phosphate-rich phases [NaCa(PO3)3 and NaPO3] for the lower calcium containing compositions, and a calcium phosphate phase [CaP2O6] for compositions with higher CaO mol%. The 55 mol% P2O5 compositions, exhibited similar phases for the lower calcium containing compositions, and a single calcium phosphate phase (CaP2O6) was identified for the higher calcium containing composition. NMR analysis revealed the presence of Q1 and Q2 species in the 45 mol% P2O5 compositions, and Q2 species present in the 50 and 55 mol% P2O5 compositions. The non-linear data obtained from the thermal and solubility analyses conducted were attributed to the packing density of the 45 mol% P2O5 compositions. The solubility was seen to decrease with increasing CaO mol%, for all the glasses investigated, and all the compositions showed a gradual decrease in pH with time, and this was accounted for by the release of Na+ and Ca2+ ions into solution.