In this paper, the influence of the stabilization temperature on the bonding configuration and the structural and textural properties of sol-gel glasses in the SiO(2)-P(2)O(5)-CaO system is presented. Raman and infrared spectroscopy are used for detecting and quantifying the local changes in the glass structural symmetry. It is demonstrated that the heat treatment leads to a repolymerization of the glass structure through condensation reactions, inducing configurational transitions from reactive chains to the more stable condensed rings. Moreover, high-resolution transmission electron microscopy analysis reveals the presence of nanocrystalline areas associated with orthophosphate groups, presenting different features depending on the stabilization temperature.