Continuous efforts are ongoing to discover new luminescent materials with appropriate properties for applications in medicine, serving as theranostic agents for healing and bioimaging. In this paper, novel single-phase carbonated calcium chlorapatite (Ca10(PO4)5(CO3)Cl2, abbreviated as CaClAp-CO3) phosphors activated with varying concentrations of Sm3+ ions were successfully fabricated using both co-precipitation and hydrothermal methods to investigate the influence of the synthesis techniques on the physicochemical properties of these materials. The effects of doping concentration of Sm3+ ions and synthesis techniques on the structure, photoluminescence (PL), energy transfer, substitute sites, fluorescence lifetime and luminescence colour of phosphors were investigated. The synthesized phosphors were characterized by X-ray diffraction (XRD) to confirm their crystal phase structure and purity. Vibrational features and the incorporation of carbonate ions were verified using Fourier-transform infrared (FTIR) spectroscopy. The obtained materials emit reddish-orange light, primarily from the most intense 4G5/2 → 6H7/2 transition. The electric dipole to magnetic dipole transition ratio (ED/MD), CIE colour coordinates and colour purity were determined to provide additional insights into the spectroscopic attributes of the obtained phosphors. In addition, the concentration quenching was also observed, and its mechanism was proposed based on theoretical calculations showing the multipolar interactions.