Various concentrations of samarium (Sm 3+ ) ion‐activated oxyfluoroborate (ANCB:AlF 3 ‐NaF‐CaF 2 ‐B 2 O 3 ) glasses are fabricated for its applications in red‐emitting lasers and scintillators. From the optical absorption spectrum, Ω 2,4,6 intensity parameters and several radiative parameters along with the high value of absorption (2.96 × 10 −21 cm 2 ) and emission (14.13 × 10 −22 cm 2 ) cross sections are calculated. By stimulating at 403 nm, a transition corresponding to 4 G 5/2 → 6 H 7/2 (596 nm) is very intense and emits orange‐reddish luminescence of Sm 3+ ion in ANCB glasses. The decay curves are fit to the Inokuti–Hirayama (I–H) model to determine the energy transfer in Sm 3+ : ANCB glasses. The X‐ray‐excited luminescence (XEL) spectra are determined with an X‐ray source by supplying the voltage of 50 kV and current 30 mA. The lasing parameters like stimulated emission cross section (14.13 × 10 −22 cm 2 ), optical gain (30.52 × 10 −22 cm 2 s), and quantum efficiency (80%) are found to be high for the 4 G 5/2 → 6 H 9/2 transition of Sm 3+ ions. The quality of the emitted red light for the ANCBSm0.5 glass is calculated in terms of the (x, y) color coordinates and correlated color temperatures (CCT < 3000 K). The integral scintillation efficiency of glasses shows the maximum value of 23% in comparison with Bi 4 Ge 3 O 12 scintillation crystal.