The possible use of bioglass as implant materials is due to its biocompatibility to human body. Even if many animal studies for the bioglasses have been performed, their structures and physical properties are not fully understood. In the present work, several investigations such as Raman spectroscopic analysis, density, thermal expansion coefficient, softening temperature, and refractive index measurement were carried out to find the structures and physical properties of bioglasses, where MgO is substituted for CaO in bioglass composition (46.1%SiO2, 24.4%Na2O, 26.9%CaO, 2.6%P2O5 ; mole%). Hydroxyapatite formation on the glass surface reacted in Tris-buffer solution was also examined. When CaO was replaced by MgO, nonbridging oxygen in glass structuer was diminished but the degree of disorder increased. Thermal expansion and softening properties showed the mixed oxide effect. Hydroxyapatite were formed on the surface of 0~11mole% of MgO containing bioglasses, and the thickness of SiO2-rich layer as well as hydroxyapatite layer were unchanged with MgO content. However, the hydroxyapatite was not formed on the surface of the bioglasses containing over 11 mole percent MgO, even if the glasses were reacted for long period.