Recent studies on silica glass as a photonic material will be described. With regard to the structural disorder, investigations have been made to improve transparency and to shift the optical absorption edge in the ultraviolet towards shorter wavelengths. Remarkable advances have been achieved in the understanding of both light scattering, which is a dominant factor in the optical losses in silica fibers, and the absorption edge. Freezing of the structural disorder was observed, and structural relaxations are found to be important for improving the transparency, whereas for the absorption edge thermal vibration effects seem to be more predominant than the structural disorder. From the results, the present authors have tried to control the structural relaxation for developing silica glass with an ultimate optical transparency, finding that a very tiny amount of the proper impurity species gives rise to structural subrelaxations, which are effective in reducing the Rayleigh scattering. The scattering was reduced by 13% by addition of only 10 wt.ppm Na2O, for example.