We have extended the usefulness of bioactive glass-ceramics for the repair and reconstruction of hard tissues by introducing F ions that are known to be beneficial, especially in dentistry. Nano-macro multimodal porosity in soda-lime phosphofluorosilicate bulk samples was introduced by the recently developed melt-quench-heat-etch method. The choice of starting glass composition is based on 48SiO2-2.7P2O5-xCaF2-yCaO-zNa2O where x = 0, 1, 4, 8, 10, 12, and (y + z) = 49.3-x (mol%). The effect of thermal and chemical treatment on the microstructure of samples is characterized by SEM, XRD and EDX. We find the formation of many crystalline phases, but mainly sodium calcium silicate, calcium phosphate, fluorapatite and calcium silicate. The bioactivity of soda-lime phosphofluorosilicate glass-ceramics is assessed by monitoring the formation of hydroxyl apatite (HA) layer: fluorapatite phase accelerates the rate of HA layer formation; the initial composition and multi-modal porosity are other key parameters that impact the formation of HA. The present porous glass-ceramics should be superior candidates for use in dental bone regeneration.