Today, silicate photothermorefractive (PTR) glasses are well known as a holographic medium for fabrication of holographic volume diffractive optical elements. The photothermoinduced crystallization process is used for recording high-efficiency phase volume holograms in this material. These holograms are used for developing unique diffractive optical elements that provide new opportunities for the laser technique, for example, narrowband filters for solid-state lasers and laser diodes, beam combiners, holographic collimator sights, chirped gratings for laser pulse compression, etc. By now, the photothermoinduced crystallization and properties of the PTR glass are investigated well enough. However, there are some issues and features still, which are solved in the present work. The mechanism of refractive index change in fluoride photothermorefractive glass during photothermoinduced crystallization and refractive index profile of the volume Bragg gratings were discussed. We studied a fine structure of a core-shell system inside fluoride PTR glass in which a silver nanoparticle presents the core and crystalline phases of silver bromide and sodium fluoride present the shell. We report on the optical properties of volume Bragg gratings in chloride PTR glass after femtosecond laser bleaching. We demonstrated that the bleaching procedure significantly reduces the absorption and increases the thermal stability of the Bragg gratings.