Abstract <p>Hydroxyapatite is one of the main inorganic biocompatible materials used in orthopedics and dentistry as a therapeutic drug. Hydroxyapatite doped with ions of rare earth elements is widely used in biomedicine to visualize the processes occurring in biological objects, acting as a biological probe. At the same time, it is necessary that the doped hydroxyalpatite be nontoxic and have a high yield of photoluminescence (fluorescence), which is not absorbed in the tissues of the biological object. In this regard, there is a need to study different methods of synthesis and doping of hydroxyapatite. In this work, the doping of hydroxyapatite (HA) with Eu³⁺ ions and together with Eu³⁺ and Dy³⁺ ions was investigated. Doping was carried out by high-temperature annealing (<i>T</i> = 20–1350°C) of a mixture of hydroxyapatite powder Ca₅OH(PO₄)₃ with powders of europium oxides Eu₂O₃ and dysprosium Dy₂O₃. To determine the optimal annealing temperature at which the maximum fluorescence intensity is achieved, annealing was carried out in stages, at different temperatures of 800, 945, 1200, and 1350°C in a vacuum furnace at the residual gas pressure in the chamber <i>P</i> = 13&#xa0;Pa. The change in the structure of hydroxyapatite as the annealing temperature increases and luminescence centers in hydroxyapatite form as a result of thermal diffusion of Eu³⁺ and Dy³⁺ ions from the corresponding europium oxides Eu₂O₃ and dysprosium Dy₂O₃ into the structure of hydroxyapatite was recorded using photoluminescence and Raman spectra. A 405 nm diode laser was used to excite the photoluminescence spectra. The excitation of the Raman spectra was carried out by a laser at a wavelength of 785 nm. Hydroxyapatite doped with Eu³⁺ and Dy³⁺ ions with pronounced photoluminescence at a wavelength of 573 nm was obtained by high-temperature annealing.</p>