Europium-substituted copper-doped calcium hydroxyapatites with common chemical composition Ca10-xEux(PO4)6O2H2–x–y–δCuy (x = 0.23–0.42; y = 0–0.27) were synthesized via solid state reaction. Obtained materials were analyzed by powder XRD, UV–Vis, Raman, luminescence spectroscopy, and colorimetry. Crystal structure characterization (including unit cell parameters, atomic positions, and position occupancies) was provided using the Rietveld refinement method in the P63/m space group. It was established that europium ions occupied the Ca(2) position only and the copper ions were located at the (0,0,0) position inside the hexagonal channel. Europium-substituted copper-doped apatites exhibit light pink color in comparison with the bright red-violet europium-free copper-doped calcium hydroxyapatite. Adversely to the europium-free samples europium-substituted, samples show the visible orange-red luminescence. Versatile analysis of the obtained materials showed that they are promising to be used as the low-toxic inorganic pigments with additional luminescent properties.