Sol-gel derived porous bioactive glasses were prepared by using the dual-templating method.  Block copolymers used as one template component produced mesopores and the polymethyl methacrylate (PMMA) colloidal crystals as the other template component yielded three-dimensionally ordered macroporous bioactive glasses (3DOM-BG). The dual-templating 3DOM-BG with two different compositions exhibited greater weight loss in thermogravimetric analysis (TGA) and larger heat release in the major exothermic peak in differential thermal analysis (DTA) than the single-templating counterparts. It can be concluded that 3DOM-BG have higher crystalline phase and moisture absorption in their scaffolds.