Bioactive glass powders, with a composition of SiO 2-CaO-P 2O 5, have been successfully synthesized via a sol-gel process at considerably lower temperatures than required for conventional melting methods. Bioactive glass powders made via conventional methods form an interfacial bond with bone when they are implanted. Bonding is correlated with the formation of a surface hydroxyapatite layer. This study examined the formation of a hydroxyapatite layer in Tris-buffered solution as a function of SiO 2 content of sol-gel derived powders. A FT-IRRS technique was used to monitor the formation of the hydroxyapatite on the surface of the powders. X-ray diffraction analysis and BET were also used to characterize the chemical and physical properties of the sol-gel derived bioactive powders. It was discovered that: (a) the rate of hydroxyapatite formation decreased with increasing SiO 2 content for powders whose SiO 2 content was less than 90 mol%; (b) a hydroxyapatite film does not form for the powders whose SiO 2 content is more than 90 mol%; (c) the SiO 2 limit, beyond which the powders lost their bioactivity, was much higher for bioactive glass powders made through sol-gel process (90%) than those made by conventional melting methods (60%). These results indicate that it is possible to significantly expand the bioactive composition range through microstructural control made possible by sol-gel processing techniques.