There have been many studies on the biological phenomena of Bioglasses, which nay be used as implant materials in human body. However, not many works on the Bioglass compositions have been reported. In the present study, the effect of Al2O3 substitution for SiO2 in Bioglass of Na2O-CaO-P2O5-SiO2 system on its structure and properties was examined. Infrared and Raman spectroscopic studies for the glass structural analysis, differential thermal analysis and X-ray diffraction analysis for crystallization of the glass were perfomed. Several physical properties, such as thermal expansion coefficient, softening point, microhardness and reaction phenomena, were also measured. The major crystalline phase, after heat treatment of the glasses, was Na2Ca2(SiO2)3 and the crystal was transformed into other phase with increased substitution of Al2O3. The added Al2O3 reduced non-bridging oxygen in glass structure and thermal expansion coefficient, but increased glass density, sofening point and microhardness. When the glasses are reacted in Tris-buffer solution, the substituted Al2O3 inhibited the formation of hydroxyapatite on the Bioglas surface, and no hydroxyapatite was formed for the sample which contained more than 6wt.% of Al2O3 even if they were reacted for 600 hours.