The structure of glasses in the system Ca(PO3)2– NaPO3–B2O3 has been investigated using Raman and NMR (31P MAS, 11B) measurements. For calcium borophosphates of composition (1-x)Ca(PO3)2.xB2O3 (0£x£0·6), structural models are proposed for glasses of varying x. In the phosphate rich compositional domain (