It has been proposed that the Cao-$SiO_2$ binary system can be good basic composition of bioactive glasses and glass-ceramics. In the present study, various kinds of Cao-$SiO_2$ gels were prepared by sol-gel method in order to control the microstructure which are related to their dissolution rate, induction period of apatite formation in body environment. Characterization of the gels were done by wet chemical analysis, SEM observation, FT-IR spectroscopy and XRD. The gelation time decreased with CaO content. However, the volume of all the dried gel decreased to 50% of the wet gels irrespective of increasement of CaO content. All the Cao-$SiO_2$ gels were amorphous and contained a large amount of silanol groups on their surfaces after heat treatment up to $800^{circ}C$. The interconnected structure of the gel changed to agglomerated spherical powders when Ca content exceed to 20 mol%. Most of the Cao-$SiO_2$ gel showed amorphous when heat-treated up to $900^{circ}C$. However, quartz and cristobalite was produced when heat-treated at $1000^{circ}C$ and resultant microstructure of the gel contained microporous structure.