Sb 31 -doped and (Sb 31 ,Mn 21 )-co-doped calcium hydroxyapatites were synthesized from a hydrothermal system, and the photoluminescent properties of these materials were investigated. The position of the emission peak of Sb 31 varies significantly with the amount of F 2 and Cl 2 anions and the F 2 /Cl 2 ratio in the reaction system. Energy transfers from Sb 31 to Mn 21 in the as-synthesized (Sb 31 ,Mn 21 )-co-doped hydroxyapatite compounds have been observed. No reducing atmosphere is needed to prevent the oxidation of Mn 21 ions in the hydrothermal synthesis of the (Sb 31 ,Mn 21 )-co-doped calcium hydroxyapatite.