Sm3+ doped lithium borate (LB) glasses with compositions (in mol %) (60-x) B2O3+ 20LiF + 10MgF2 + 10ZnO + xSm2O3 (where x = 0.1, 0.5, 1.0, 1.5 and 2 mol%) have been prepared by melt quenching technique and have been investigated using thermal measurements, optical absorption, luminescence, and decay kinetic techniques as well as Judd–Ofelt (J–O) analysis. The thermal stability of host glass system can be accessed from differential thermal analysis (DTA) measurements. For these glasses X-ray diffraction (XRD), optical absorption, emission and decay measurements were carried out. The glassy nature of the present glass matrices were confirmed by XRD profiles. From the optical absorption spectra, the spectral intensities (f) and Judd-Ofelt intensity parameters, Ωλ (λ= 2, 4, 6) have been evaluated. From the photoluminescence spectra and using Judd-Ofelt intensity parameters, radiative transition probabilities (AR), experimental branching ratios (βexp) and stimulated emission cross-sections (σP) are calculated. To investigate luminescence efficiency of 4G5/2 level of Sm3+ doped different lithium borate glasses, lifetimes (τexp) are predicted from decay curve analysis for all prepared glass matrices. Finally, these observed results are discussed and compared with the literature data and suggested for the optical applications.