Hierarchically mesoporous-macroporous bioactive glass ceramic beads with well interconnected pore structures were fabricated in hydrophobic solvent, chloroform, by the triblock copolymer templating and sol-gel techniques. The beads have oblong pore structure with a size of several hundreds mu m and these macropore are comprised of several tens of mu m pores, several of mu m pores, and several tens of nm pores. The beads show superior apatite-like layer forming activity and good in vitro biodegradability. This simple synthetic method can be adapted for the purpose of preparing various ceramics with hierarchical pore structures, which have excellent potential applications in the field of not only biomaterials such as tissue engineering and drug storage but also catalysis, filters, adsorbents, and optics. (C) 2009 Elsevier B.V. All rights reserved.