Fluoride (F) is important for enhancing illogical activity of bioceramics. To increase fluoride content of derived Hench bioactive glass (BaG), bioactive fluorosilicate glasses (BaG-Fx) were synthesized by using melting method and characterized using different physico-chemical analyses. Fluoride-containing BaGs were synthesized at a temperature of 1350 degrees C. Structural and thermal effect of calcium fluoride (CaF2) insertion into the glass network in the BaG: SiO2-CaO-Na2O-P2O5 quaternary system was studied. Indeed, the incorporated amounts of fluorine (CaF2) (from 5% to 20% by mass) induced significant physico-chemical changes. Through the structural study by X-ray diffraction (XRD), the amorphous character of our fluorosilicate glasses is proven. Infrared (IR) spec-troscopy proved the incorporation of fluorine into the glass matrix. In the microstructural framework, we revealed the morphological changes of the glass powders as a function of the CaF2 content. These results were confirmed by Brunauer, Emmett and Teller (BET) measurements. Through Differential Scanning Calorimetry (DSC) thermal analysis we established the impact of fluoride ions on the structural dynamics and thermodynamic properties of these newly developed bioactive glasses. Accordingly, it was possible for the first time to incor-porate as much as 20 wt% of CaF2 in BaG respecting the conditions of bioactivity and biodegradability required by Hench. After detailed analyses of the transformation entropies of BG-Fx as a function of the added CaF2 content, it can be stated that the intermolecular movements within the fluorosilicate network are more limited as a function of the added CaF2 amount. This slows down the ion exchange phenomena and subsequently the dissociation of the material in vitro, which can be anticipated to occur after implantation in vivo.