The theoretical ferroelectric polarization of the low-temperature (monoclinic, P2 1 ) phase and the hightemperature (hexagonal, P6 3 ) phase of hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 is calculated based on the density functional theory (DFT). In the monoclinic structure, the value of ferroelectric polarization is found to be 9.87 mC cm À2 along the [001] direction. In the hexagonal structure, the ferroelectric polarization is 7.05 mC cm À2 along the [001] direction. The main contribution to the electric polarization comes from ordered hydroxyl OH À anions for both phases, although the inorganic Ca 5 (PO 4 ) 3 apatite framework also gives a non-negligible contribution. A detailed analysis of ferroelectric polarization and structural change of the hydroxyapatite is presented for a better understanding of this important biomaterial.