Porous materials of β-tricalcium phosphate (β-Ca3(PO4)2; β-TCP) were prepared from porous hydroxyapatite (Ca10(PO4)6(OH)2; HA) with calcium deficient composition of Ca/P molar ratio of 1.50 synthesized by hydrothermal method. The porous β-TCP was composed of rod-shaped particles of about 10-20 μm in length. Rod-shaped particles were locked together to make micro-pores, and the size of micro-pores formed by tangling of rod-shaped particles was about 0.1-0.5 μm. The particle size and micro-pore size could be controlled by our unique method. It must be suitable for the bone graft material and as the scaffold of cultured bone.