AbstractBioactive glasses convert to a biomimetic apatite when in contact with physiological solutions; however, the number and type of phases precipitating depends on glass composition and reactivity. This process is typically followed by X-ray diffraction and infrared spectroscopy. Here, we visualise surface mineralisation in a series of sodium-free bioactive glasses, using transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDXS) and X-ray nano-computed tomography (nano-CT). In the glasses, the phosphate content was increased while adding stoichiometric amounts of calcium to maintain phosphate in an orthophosphate environment in the glass. Calcium fluoride was added to keep the melting temperature low. TEM brought to light the presence of phosphate clustering and nearly crystalline calcium fluoride environments in the glasses. A combination of analytical methods, including solid-state NMR, shows how with increasing phosphate content in the glass, precipitation of calcium fluoride during immersion is superseded by fluorapatite precipitation. Nano-CT gives insight into bioactive glass particle morphology after immersion, while TEM illustrates how compositional changes in the glass affect microstructure at a sub-micron to nanometre-level.