Bioglasses have been known to be as one of the promising biomateials, which can be used for replacing defective hard and soft tissue. There have been many reports on biological results for this type of glass, but no systematic work has carried out on the structures and properties of the bioglass itself. In the present study, the effect of P2O5 in bioglasses on their structures and properties was examined. Infrared and Raman spectroscopy for the glass structural analysis, differential thermal and X-ray diffraction analysis for the crystallization of the bioglass were performed, and several physical properties were measured. When the glasses were heat-treated, Na2O.2CaO.3SiO2 was the major crystalline phase and $eta$-NaCaPO4 crystal was found for the glass with high P2O5 content. The added P2O5 in the glasses enhanced the polymerization of silicate glass structure and it changed the chain-like glass structure to a sheet-like structure, and some P2O5 may stay as phosphate monomer. With addition of P2O5 in the glass the density of the glasses decreased, but not much changes in their thermal expansion coefficient, softening point and microhardness were observed.