Hierarchically porous hydroxyapatite (HHA) scaffolds were synthesized by template-assisted sol-gel chemistry. Polyurethane foam and a block copolymer were used as templates for inducing hierarchically porous structures. The HHA scaffolds exhibited open porous structures with large pores of 400-600 µm and nanoscale pores of ~75 nm. In comparison with conventional hydroxyapatite (CHA), HHA scaffolds exhibited significantly higher surface areas and increased protein adsorption for bovine serum albumin and vitronectin. Both the HHA and CHA scaffolds exhibited well in vitro biocompatibility. After 1 day, Saos-2 osteoblast-like cells bound equally well to both HHA and CHA scaffolds, but after 7 days in culture, cell proliferation was significantly greater on the HHA scaffolds ( < 0.01). High surface area and hierarchical porous structure contributed to the selective enhancement of osteoblast proliferation on the HHA scaffolds.