Recent studies on two aspects of silica glass as a photonic material will be described. Part A of this review will be focused on structural disorder and structural relaxations in silica glass. 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. In part B of this review the second-order optical nonlinearity induced in Ge-doped silica glass will be described based on recent experiments carried out by the group of present authors. A large second-order optical nonlinearity has been successfully induced in the glass by simultaneous applications of a high dc electric field and ultraviolet (UV) irradiation, so-called UV poling. The nonlinearity induced by UV poling in bulk and film samples has achieved a magnitude of χ(2), comparable to or even larger than those of LiNbO3 and other crystals. Surprisingly enough, the nonlinearity induced by this method then decays after the UV poling as an exact single-exponential function of time, very much unlike the usual decay processes observed in glasses. Evidence is presented associating the nonlinearity with GeE′ defect centers created from oxygen deficient vacancies through photochemical reactions. The decay or degradation can be made much slower with the addition of proper impurities which work as electron scavengers. In addition, we have found that crystallites are generated in the glass by the UV poling, which leads to an increase in the third-order nonlinearity, χ(3), approximately 15 times larger than before the treatment. As a whole, the evidence strongly suggests that a major origin of the second-order nonlinearity induced in the glass is a combined effect of a large third-order nonlinearity associated with the crystallites and an internal space-charge field, where the charges to build up the field are produced during the formation of GeE′ centers. © 2000 American Institute of Physics.