A class of melt quenched silicate glasses, containing calcium, phosphorus and alkali metals, and having the ability to promote bone regeneration and to fuse to living bone, is produced commercially as Bioglass. The changes in structure associated with reacting the bioglass with a body fluid simulant (a buffered Tris(hydroxymethyl)aminomethane growth medium solution or a blood plasma-like salt simulated body fluid) at 37°C have been studied using both high energy and grazing incidence x-ray diffraction. This has corroborated the generic conclusions of earlier studies based on the use of calcia–silica sol-gel glasses whilst highlighting the important differences associated with glass composition; the results also reveal the more subtle effects on reaction rates of the choice of body fluid simulant. The results also indicate the presence of tricalcium phosphate crystallites deposited onto the surface of the glass as a precursor to the growth of hydroxyapatite, and indicates that there is some preferred orientation to their growth