The 70TiO 2 .30P 2 O 5 (mol%) glass was prepared by the sol-gel method. Its structure was examined by means of IR, Raman spectroscopy and X-ray radial distribution function analysis, and was compared with the corresponding melt-derived glass. It was found that average coordination number of Ti 4 + ions was almost 6 and Ti 4 + ions formed predominantly TiO 6 octahedra in the sol-gel-derived glass, while Ti 4 + ions were present in the 4, 5 and/or 6-fold coordination states to give average coordination number in-between 4 and 5 in the melt-glass. The preference of high coordination state of Ti 4 + ions in the sol-gel glass was consistent with higher refractive index and density than the melt-glass.