The present paper is interested in the study of compounds from the apatite family, which is an apatite structure of individual rare earth substituted fluorapatite. In fact, an Sm-Bearing fluorapatite Ca10–2yNaySmy(PO4)6A2 with x = 0.11 and y = 0.23 has been synthesized by solid-state reaction and characterized by X-ray powder diffraction. The site occupancies of substituents are 0.01091 for Sm and 0.02601 for Na in the Ca(1) position and 0.05317 for Sm in the Ca(2) position. Besides, the observed frequencies in the Raman and infrared spectra were explained and discussed on the basis of unit cell group analyses and in comparison with fluorapatite and other fluorapatites. In addition to the proton conduction, the possibility of a Na+ contribution to the conductivity in the high-temperature phase is proposed. The highest overall conductivity values were found at σ475 °C = 2.03 × 10−5 S cm−1 and Ea = 0.60 eV.