Holographic and direct-written structures are fabricated in tin-doped silicophosphite thin plates containing rhodamine 6G dye by a photothermal process based on the principle of glass softening/frozen-in behavior. To be highly processable by photothermal treatment and stable at room temperature after processing, the intrinsic viscoelastic property is improved by increasing the crosslinking density of the network structure, and the photothermal conditions for efficient transfer of the irradiated photons to thermal phonons are explored. Then, the excellent rewritability and reliability of the fine processed structure are found by examining the writing/erasing repetition. Furthermore, the origins of the changes in refractive index due to photothermal treatment are classified into density change and photobleaching, and the dynamics of the formation process of holographic gratings are studied by measuring refractive index changes as functions of irradiation time and wavelength. As a result, it is found that the holographic structure consists of spatial modulation of the refractive index and the refractive index change results primarily from the change in the frozen structure, although there is a slight influence by photobleaching.