The distinctive set containing Sm3+ ions doped LiF incorporated Alkaline borate glasses have been synthesised via the melt quenching practice. 59B2O3+20LiF+(20–X)CaCO3+XBaCO3 +1Sm2O3 (where X = 5, 10, 15, 20 wt%) is the composition used for the glass preparation. The effect of samarium ions concentration dependency on the absorption and emission of barium and calcium oxide has been studied through several spectroscopic studies. The current set of glasses is ionic, determined by the bonding value. The hypersensitive absorption transition is found in the visible region of the absorption spectra, and the transition from 6H5/2 to 6P3/2 shows the highest oscillator strength of 14.87 × 10−6. The intensity parameters are denoted by Ωλ (where λ = 2,4,6) are assessed and discussed. The results indicate that Ω4 is higher when compared to the other two parameters. The lower Ω2 values further ensure the ionic nature of the glass samples. Moreover, the intensity parameters are utilised to predict some radiative properties for the lasing potential evaluation, which includes cross-sections of emission (σPE), probability of radiative transition (A), and experimental and radiative lifetime (τexp and τR). The decay profile was monitored for the 4G5/2 state, and consistently non-exponential behaviour was observed in all the glasses. Through the CIE colour chromaticity analysis, the CCT (colour-correlated temperature), dominant wavelength, colour, and purity of the emitted light have been evaluated. Concerning all aspects, the glass with 20 wt% of BaCO3 is found to be fit for photonic and optoelectronic applications.