Herein we report for the first time the synthesis of three-dimensional scaffolds in the binary system SiO2–P2O5 exhibiting different scales of porosity: (i) highly ordered mesopores with diameters of ca. 4 nm; (ii) macropores with diameters in the 30–80 μm range with interconnections of ca. 2–4 and 8–9 μm; and (iii) ultra-large macropores of ca. 400 μm. The hierarchical porosity of the resulting scaffolds makes them suitable for bone tissue engineering applications. The chemical nature and mesoporosity of these matrices would allow these scaffolds to act as local controlled delivery systems of biologically active molecules, such as certain drugs to…