Three-dimensional, highly ordered macroporous frame of hydroxyapatite has been fabricated via a template-assisted colloidal processing technique. In the present method, colloidal template was first prepared with SiO(2) spheres by gravitational sedimentation, which was then infiltrated with hydroxyapatite precursor prepared by the sol-gel process. The resulting hydroxyapatite replicated the three-dimensionally ordered macroporous structure of SiO(2) template. Modified by H(2)O(2)- the SiO(2) spheres Could be packed into better ordered templates. After removal of the template by immersing in NaOH solution, the well-ordered macroporous frame made from HA was obtained. The arrangement of the pore structure was hexagonal close-packed and pore sizes could be controlled by changing the sizes of SiO(2) spheres. The resulting highly ordered macroporous frame of hydroxyapatite could have potential applications in the biomedical field. (C) 2008 Elsevier Ltd. All rights reserved.