Europium-doped hydroxyapatite Ca10(PO4)6(OH)2 (3% mol) powders were synthesized by an optimized chemical precipitation method at 25 °C, followed by drying at 120 °C and calcination at 450 °C and 900 °C. The obtained nanosized crystallite samples were investigated by means of a combination of inductively coupled plasma (ICP) spectroscopy, powder X-ray diffraction (PXRD), Fourier Transform Infrared (FTIR), Raman and photoluminescence (PL) spectroscopies. The Rietveld refinement in the hexagonal P63/m space group showed europium ordered at the Ca2 site at high temperature (900 °C), and at the Ca1 site for lower temperatures (120 °C and 450 °C). FTIR and Raman spectra showed slight band shifts and minor modifications of the (PO4) bands with increasing annealing temperature. PL spectra and decay curves revealed significant luminescence emission for the phase obtained at 900 °C and highlighted the migration of Eu from the Ca1 to Ca2 site as a result of increasing calcinating temperature.