Molecular dynamics simulations of four bioactive silicate glasses containing between 0 (P0) and 12 (P12) mol % P2O5 have been carried out in order to elucidate the structural role of phosphorus in these materials. In particular, we have focused on structural features which can have a direct role in the bioactive mechanism of dissolution and bone bonding. The higher affinity of modifier Na and Ca cations for coordinating phosphate rather than silicate, together with the formation of P-O-Si linkages, lead to increasing repolymerization of the silicate network with increasing P2O5 content, which in principle would represent a negative effect of P inclusion on the glass bioactivity. However, this effect is counterbalanced by the concomitant increase in the amount of free orthophosphate groups, whose fast release is deemed to enhance the bioactivity. The strong affinity of the orthophosphates for calcium ions leads to a clear tendency toward separation of silicate-rich and phosphate-rich phases for the P12 composition. Although this could reduce the bioactivity in the case of P12, in general, the favorable balance between the effects mentioned above should result in a positive effect of partial Si -> P substitution on the glass bioactivity.