Sb³⁺-doped and (Sb³⁺,Mn²⁺)-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 Sb³⁺ varies significantly with the amount of F⁻ and Cl⁻ anions and the F⁻/Cl⁻ ratio in the reaction system. Energy transfers from Sb³⁺ to Mn²⁺ in the as-synthesized (Sb³⁺,Mn²⁺)-co-doped hydroxyapatite compounds have been observed. No reducing atmosphere is needed to prevent the oxidation of Mn²⁺ ions in the hydrothermal synthesis of the (Sb³⁺,Mn²⁺)-co-doped calcium hydroxyapatite.