Studies of the temperature dependence of the electrical properties of glasses show that the high-temperature annealing in glasses observed irreversible processes. These processes lead to changes in electrical conductivity, dielectric permittivity, and hence the electrical capacitance, dielectric loss tangent, and other parameters. Obviously, this is due to structural changes in the glass as a result of high-temperature annealing. In this regard, this paper presents studies of structural and phase transformations in glasses used for the production of microchannel plates in the process of high-temperature annealing in vacuum and in the air atmosphere at different times. The studies were conducted by x-ray phase and X-ray diffraction analysis, as well as X-ray fluorescence elemental analysis.