In the present research work, glass powders and three different organic starches were used to realize macroporous glass-ceramic scaffolds for bone substitutions. For this purpose, bioactive glass powders belonging to the system SiO2-CaO-Na2O-MgO were mixed in a liquid medium with the desired amount of the selected organic phase. Afterwards, by progressively raising the temperature, the water uptake of starches occurred and led to the gelling of the whole system. The resultant gel underwent two thermal treatments in order to eliminate the organic phase and to allow the sintering of the glassy phase. In this way, macroporous glass-ceramic scaffolds were successfully prepared. The samples were characterized by means of optical and scanning electron microscopy with compositional analysis. The volume and mean size of the obtained porosity were investigated by means of mercury intrusion porosimetry, whereas its morphology was assessed by means of microscopic observations. The structure of the original and the resultant materials were investigated by X-ray diffraction. In order to study the reactivity of the scaffolds towards physiological media, the samples were soaked in a simulated body fluid for various times. On their soaked surfaces, scanning electron microscopy and compositional analysis were carried out in order to assess their bioactivity.