This article reports a comparison of the structural and textural properties of bioglass-hydroxyapatite (HA) composites obtained in the SiO(2)-CaO-P(2)O(5) system by sol-gel method, with different amounts of hydrogen peroxide (3% H(2)O(2)) or water (H(2)O). X-ray diffraction, Raman, and FT-IR spectroscopy reveal the presence of nanocrystalline HA. Scanning electron microscopy images illustrate that the HA phase is mainly distributed on the glass surface. The results point out that the sintering at 550 degrees C of a sol-gel derived SiO(2)-CaO-P(2)O(5) bioglass leads to a single crystalline phase of HA, and validate a new processing method for obtaining bioglass-HA composites. Structural analyses of the investigated composites indicate the existence of a silicate network built up from Q(3) and Q(2) units. The replacement of water with hydrogen peroxide has as consequence the increase of depolymerization degree of silica network. Textural properties were investigated with N(2)-adsorption technique. The composites prepared with hydrogen peroxide exhibit a more uniform and narrow mesoporous distribution that recommends them for drug uptake and release applications. It was found that the specific surface area and pore volume are clearly influenced by the H(2)O(2)(H(2)O):TEOS molar ratio.