The sol–gel process of producing SiO2–CaO bioactive glasses is well established, but problems remain with the poor mechanical properties of the amorphous form and the bioinertness of its crystalline counterpart. These properties may be improved by incorporating Na2O into bioactive glasses, which can result in the formation of a hard yet biodegradable crystalline phase from bioactive glasses when sintered. However, production of Na2O-containing bioactive glasses by sol–gel methods has proved to be difficult. This work reports a new sol–gel process for the production of Na2O-containing bioactive glass ceramics, potentially enabling their use as medical implantation materials. Fine powders of 45S5 (a Na2O-containing composition) glass ceramic have for the first time been successfully synthesized using the sol–gel technique in aqueous solution under ambient conditions, with the mean particle size being ∼5 μm. A comparative study of sol–gel derived S70C30 (a Na2O-free composition) and 45S5 glass ceramic materials revealed that the latter possesses a number of features desirable in biomaterials used for bone tissue engineering, including (i) the crystalline phase Na2Ca2Si3O9 that couples good mechanical strength with satisfactory biodegradability, (ii) formation of hydroxyapatite, which may promote good bone bonding and (iii) cytocompatibility. In contrast, the sol–gel derived S70C30 glass ceramic consisted of a virtually inert crystalline phase CaSiO3. Moreover, amorphous S70C30 largely transited to CaCO3 with minor hydroxyapatite when immersed in simulated body fluid under standard tissue culture conditions. In conclusion, sol–gel derived Na2O-containing glass ceramics have significant advantages over related Na2O-free materials, having a greatly improved combination of mechanical capability and biological absorbability.