Glasses with compositions (100-x)SiO(2)-xHfO(2):0.3Eu(3+) (molar ratio, x=0,10,20,30) for optical applications were prepared using the sol-gel route. The introduction of hafnium into the glass matrix induced the energy splitting of the F27 state of Eu(3+) ions. Furthermore, fluorescence line narrowing (FLN) spectra indicated that Eu(3+) clustering occurred in glasses containing no hafnium. The addition of hafnium promoted better dispersion of Eu(3+) ions in the glass matrix. The role of hafnium on modifying the properties of glasses was discussed with respect to x-ray diffraction and FLN analysis.