Glasses and glass-ceramics of the system Diopside [D, CaMgSi2O6] - Fluorapatite [FAp, Ca5(PO4)3F] were synthesized and characterized. The studied theoretical phase compositions were (wt%): 1) 70% D-30% FAp, 2) 60% D-40% FAp and 3) 80% D-20% FAp. The glass-ceramics were synthesized by isothermal treatment of the corresponding parent glasses at either 800, 900 or 1000 °C, with holding times of either 30 min, 2 h or 5 h at high temperature. The in vitro bioactivities of all materials were tested in Kokubo’s Simulated Body Fluid (SBF), for 21 days at pH = 7.4 and 37 °C. All materials were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM/EDS). In all cases, the in vitro bioactivity increased with decreasing crystallization degree in the materials, which was likely due to an inhibitory effect of the structural changes occurring during thermal treatment of the glasses. This was more accentuated for long thermal treatments. After 21 days of soaking in the SBF, an apatite-like surface layer, with a Ca/P molar ratio close to 1.67, was formed in the case of the parent glass of composition 2. This was attributed to an enhancing effect of so-called “phase separation” phenomenon that took place during the synthesis of that particular glass. Lastly, the MgO content of the glasses made no clear difference on their in vitro bioactivity.