Transparent bubble free phosphate glasses having a composition 40Na(2)O-10Al(2)O(3)-xTiO(2)-(50-x)P2O5 (x = 0-20 mol%) were prepared by melt quench method and characterized for their optical, thermo-physical and structural aspects. Substitution of TiO2 for P2O5 up to 10 mol% in the ternary 40Na(2)O-10Al(2)O(3)-50P(2)O(5) glass increases the density, glass transition temperature (T-g), microhardness (MH), and decreases the molar volume, thermal expansion coefficient, and optical gap (E-optical). Further substitution of TiO2 results in the decrease of density, T-g, and MH. Based on the P-31 magic angle spinning nuclear magnetic resonance and Fourier transform infrared spectroscopy, it is established that up to 10 mol% TiO2 incorporation in the glass, the network undergoes only a slow depolymerization while forming P-O-Al and P-O-Ti linkages. Variation in optical properties like Eoptical and wavelength corresponding to emission maxima indicates that up to 10 mol% incorporation, TiO2 acts as a network modifier and above that it forms a network of Ti-O-Ti linkages connected with discrete PO4 structural units. Thus, the variation in the thermo-physical and optical properties has been explained by the composition-dependent structural changes brought about by TiO2 in the glass matrix.