The three-phase of SiO2-CaO-P2O5 bioactive glass was successfully fabricated with three dimensionally ordered macroporous (3DOM) structure by incorporating a colloidal crystal template in the sol-gel synthesis. Whereas the composition and purification of all four- and five-phase bioactive glasses were obtained after the inclusion of sodium nitrate and ferric nitrate nonahydrate, the phase additions resulted in the deformation of the scaffolds and the curved walls were thinner with larger variations in size. Such difference was due to the gel-coating on spherical crystals instead of the filling in the interstitial holes of the template. Moreover, the bioactive glass microspheres were formed on the surface of the scaffolds due to the strong precursor-template interactions. Nevertheless, the five-phase bioactive glasses exhibited the thermal stability up to 1000 oC with slight mass loss and heat transfer.