We report here the luminescence spectra of certain rare earth ions (Eu 3+ , Tb 3+ & Ho 3+ ) doped B 2 O 3 -BaO-LiF/AiF 3 based on the measurements of emission and decay curves of prominent emission transitions. For both the reference host glasses, FTIR, XRD, DTA-TG profiles have been recorded to understand their structural and thermal properties. Eu 3+ doped glasses have shown five emission transitions of 5 D 0 → 7 F 01,2,3 & 4 located at 580nm, 593nm, 615nm, 655nm and 704nm respectively with an excitation at λ exci = 392 nm ( 7 F 0 → 5 L 6 ). Also under an UV source, these europium glasses have displayed a bright red emission from their surfaces. Tb 3+ glasses have exhibited four emission bands of 5 D 4 → 7 F 6,5,4,3 at 491nm, 547nm, 588nm and 625nm respectively with an excitation at λ exci = 376 nm ( 7 F 6 → 5 G 6 ). Intense green emission from the glass surfaces has been noticed upon exposure to the UV source. Prominently bluish-green emission has been noticed from the surfaces of the holmium glasses under an UV source and same emission transition ( 5 F 4 → 5 I 8 ) at 519 nm with an excitation at λ exci = 389 nm ( 5 I 8 -5 G 4 ) has also been obtained from their measured emission spectra. For all the prominent emissions of the rare earth glasses, decay curves have been measured to compute their lifetimes.