[en] The present paper brings out the results concerning the preparation and optical properties of Sm³⁺ and Dy³⁺ each ion separately in four different concentrations (0.1, 0.5, 1.0 and 1.5 mol%) and also together doped (1 mol% Dy³⁺+x mol% Sm³⁺): Li₂O–LiF–B₂O₃–CdO (where x=0.1, 0.5, 1.0 and 1.5 mol%) glasses by a melt quenching method. Sm³⁺ doped base glasses have displayed an intense orange emission at 602 nm (⁴G_5/2→⁶H_7/2) with an excitation at 403 nm and Dy³⁺ doped glasses have shown two emissions located at 486 nm (⁴F_9/2→⁶H_15/2; blue) and 577 nm (⁴F_9/2→⁶H_13/2; yellow) with λ_exci=387 nm. The co-doped (Dy³⁺+Sm³⁺) lithium fluoro-boro cadmium glasses have been excited with an excitation at 387 nm of Dy³⁺ which has resulted in with a significant reduction in Dy³⁺ emission, at the same time there exists an increase in the reddish-orange emission of Sm³⁺ due to an energy transfer from Dy³⁺ to Sm³⁺. The non-radiative energy transfer from Dy³⁺ to Sm³⁺ is governed by dipole–quadrupole interactions as is explained in terms of their emission spectra, donor lifetime, energy level diagram and energy transfer characteristic factors. -- Highlights: • In co-doped (Dy³⁺+Sm³⁺): LFBCd glass, reddish-orange emission due to Sm³⁺ (⁴F_9/2→⁶H_J) has been enhanced due to an energy transfer from Dy³⁺ ions in the glass. • This has been evidenced from a lowering trend in the emission transition lifetimes of donor (Dy³⁺) ions with increasing acceptor (Sm³⁺) concentration. • Energy transfer mechanism involved in Dy³⁺→Sm³⁺ has been explained in terms of I–H luminescence decay curve analysis