Calcium carbonate (CaCO(3)) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO(3) monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO(3) monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO(2) through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8-48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.