Defect-related photoluminescence (PL) in materials have attracted interest for applications including near ultraviolet (NUV) excitable light-emitting diodes and in biomedical field. In this paper, hydroxyapatite [Ca10(PO4)6(OH)2] nanorods with intense PL bands (bluish- and yellowish-white emissions) were obtained when excited under NUV radiation at room temperature. These nanoparticles were synthesized via chemical precipitation at 90°C followed by distinct heat treatments temperatures (200–800°C). Intense and broad emission profiles were achieved at 350°C (380–750nm) and 400°C (380–800nm). UV–Vis spectroscopy revealed band gap energies (5.58–5.78eV) higher than the excitation energies (~3.54 and ~2.98eV at 350 and 415nm, respectively), confirming the contribution of defect energy levels within the forbidden zone for PL emissions. The structural features were characterized by X-ray diffraction, Rietveld refinement, thermogravimetric analysis, and Fourier transform infrared spectroscopy. By means of these techniques, the relation between structural order-disorder induced by defects, chemical reactions at both lattice and surface of the materials as well as the PL, without activator centers, was discussed in details.