The bioactivity of glasses in the CaO-SiO2 system and CaO-P2O5-SiO2 system with less than 10mol% of P2O5 was investigated by in vitro test in simulated body flood(SBF). The formation of Ca.P film and hydroxyapatite on the surface of glasses after in vitro test was analysed by X-ray photoelectron spectoscopy (XPS), fourier transform infrared reflection spectroscopy (FT-IRRS), energy dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM) observation. In the early stage of Ca.P film formation after in vitro test for CaO-SiO2 and CaO-P2O5-SiO2 glasses, the rate of Ca.P film formation on the surface of the glasses was dependent of structural parameter (Y) evaluated from the glass composition. First, in the case of the glasses having Y value below 2, Ca.P film and SiO2-rich layer were formed simultaneously, and there were no differences of the rate of Ca.P film formation in terms of the Y values. Second, in the case of the glasses having Y value above 2, the SiO2-rich layer was formed, and then Ca.P.Si mixed layer was formed in the silica gel structure of the SiO2-rich layer, and finally the Ca.P film on the surface of SiO2-rich layer. The rate of Ca.P film formation delayed as the Y values increased. The rate of hydroxyapatite formation of glasses (the rate of transformation from Ca.P film to hydroxyapatite) seems to be propotional to the rate of Ca.P film formation and Y value. The rate of hydroxyapatite formation of glasses belonging to the second group was delayed as structural parameter increased, and the hydroxyapatite crystal showed spherical growth in the early reaction stage, and then showed silkworm-like linear growth as the reaction time increased.