We report the fluorescence properties of samarium (III) ions in fluoro-borate glasses (Sm 3+ :BCNF) which were examined through X-ray diffraction, Fourier transform infrared, and UV–Vis–NIR spectroscopy. From the absorption spectra, Judd–Ofelt intensity parameters were determined, which are in turn used to evaluate several radiative properties for the various excited states of samarium (III) ions. The emission spectrum was used to calculate the effective bandwidth (Δ λ eff ) and empirical branching ratios ( β exp ). With increasing concentrations of samarium (III) ions, the luminescence decay patterns of the 4 G 5/2 transition became double exponential. The Inokuti–Hirayama model for S  = 6 has been used to explain the double-exponential behavior of decay time profiles, revealing that the energy transmission mechanism between the samarium (III) ions are dipole–dipole.