A series of Cs-phosphate glasses, xCs2O(1−x)P2O5, where 0x0.60, were prepared. The glass transition temperature (Tg) decreases with the initial addition of Cs2O to P2O5, from 637 K at x=0 to 472 K at x=0.16. There is little change in Tg with further additions of Cs2O up to x=0.60. The 31P magic angle spinning nuclear magnetic resonance (MAS NMR) spectra show that Cs2O additions systematically convert the cross-linked ultraphosphate network of ν-P2O5 to a chain-like metaphosphate structure as x approaches 0.50. The 133Cs MAS NMR spectra show a 90 ppm increase in isotropic chemical shift (δiso) with increasing Cs2O content, which indicates a decrease in the average electron density around the Cs+ ions, more covalent Cs-O bonding, and a shorter average Cs-O bond length. The physical properties and spectroscopic results are interpreted using a structural model that considers the effects of composition on the average coordination environment of Cs+ ions.