Porous CaO-P2O5-SiO2 monolithics with double-pore structure were prepared from tetraethoxysilane, triethylephosphate and calcium nitrate by a sol-gel method. Polyethylene glycol and starch were used as mesopore-making agent and as macropore-making agent, respectively. The porous monolithics, having mesopores with ~20 nm pore size and macropores with 7~20 μm pore size, could be formed from the removal of organic components after heated at 600°C for 2 hours. After soaked in simulated body fluid (SBF) at 37°C for 7 days, bonelike apatite was formed on the surface of the samples. The porous samples were degraded gradually in SBF solution.