The melt‐quenching technique is used to fabricate calcium sodium aluminum borate glasses (Sm: ANCB) doped with varying concentrations of Sm3+ ions. Characteristics of ANCBSm glasses, including density, molar volume, refractive index, absorption, emission (via visible light, X‐ray, and proton excitation), decay time, and CIE color coordinates, are analyzed. The density, molar volume, and refractive index of ANCBSm glass increased with Sm2O3 concentration. Sm3+ ions enabled photon absorption in both visible and NIR regions, with a strong reddish‐orange emission at 600 nm due to the 6H5/2 → 6P3/2 transition under various excitations. X‐ray excitation is also compared with BGO scintillation crystals. The J–O theory predicted the radiative properties of Sm3+ ion emission levels. Decay curves of the 6H5/2 levels showed a single exponential nature with a millisecond‐order lifetime. CIE chromaticity of ANCBSm glasses is in the reddish‐orange region. ANCBSm glasses have potential applications in orange laser medium material.