It has been reported that a biocement obtained by mixing CaO-SiO2-P2O5 glass powder and ammonium phosphate solution has biocompatibility as well as high strength. However, the compositional dependence on its hardening and hydroxyapatite formation phenomena has not been studied. Therefore, the main objective of this work is to study the effects of P2O5, MgO in CaO-SiO2 system glass on the hardening and hydroxyapatite formation. When more than 50 mole% of CaO containing CaO-SiO2 glasses was reacted with ammonium phosphate solution, CaNH4PO4.H2O crystal was formed, but the glass with less than 50 mol% of CaO formed (NH4)2HPO4 and NH4H2PO4 crystals which are derived from ammonium phosphate solution without reacting with the glasses. As the amount of P2O5 in CaO-SiO2-P2O5 glass system was increased, the formation of CaNH4PO4.H2O crystal was enhanced. When those hardened samples were reacted with tris-buffer solution, hydroxyapatite was obtained only for the sample with CaNH4PO4.H2O. While the substitution of MgO for CaO decreased the formation of CaNH4PO4.H2O crystal. MgNH4PO4.H2O crystla was formed in high MgO containing glass, which did not react with tris-buffer solution.