The polyhedral arrangements in xTiO2. (1-x) P2O5 (0·55≤x≤0•70) and yTiO2.(1-y)Ca(PO3)2 glasses have been characterised by Raman spectroscopy, electron spin resonance (ESR) spectroscopy, and solid state 31 P magic angle nuclear magnetic resonance (MAS NMR) spectroxcopy In the binary titanophosphate glasses, structures consist of distorted Ti octahedra linked to orthophosphate units through Ti-O-P bonds. There is evidence for Ti-O-Ti linkages in the Raman spectra from glasses with the highest TiO2 contents. When titania is added to calcium metaphosphate glass, phosphate chains are depolymerised by the incorporation of distorted Ti(5) and Ti(6) units through Ti-O-P bonds. Pyrophosphate units are present in glasses with the highest TiO2 contents.