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 compositional dependences of structures and physical properties are not fully understood. In the present work, physical property measurements such as density and thermal expansion coefficient were carried out for the bioglasses, with substitution of CaO for Na2O in bioglass composition (46.1%SiO2, 24.4%Na2O, 26.9%CaO, 2.6%P2O5:mol%). Hydroxyapatite formation on the glass surface was also examined after reacted in Tris-buffer solution. As CaO was substituted for Na2O, the bond strength between nonbridging oxygen and modifier became stronger to make glass structure rigid, and resulted in increase in density and decrease in thermal expansion coefficient. When the bioglasses were reacted in Tris-buffer solution, hydroxyapatite was formed on the bioglass surface for all prepared glasses in 2 hours, independently on CaO content, and the thickness of hydroxyapatite layer was decreased a little, while the thickness of SiO2 rich layer was decreased sharply with CaO content.