Li2O-BaO-Al2O3-La2O3-P2O5 glasses optically activated with rare earth ions with the 4f5, and 4f8 electronicconfiguration (Sm3+ and Tb3+, respectively) were analyzed by Raman spectroscopy, absorption,excitation photoluminescence, decay curves and temperature dependent photoluminescence. The spectroscopiccharacteristics of the as-prepared and heat treated samples at temperatures below and aboveTg were studied as well as their room temperature photometric properties under ultraviolet excitation.All the doped glasses exhibit typical signatures of the lanthanides in their trivalent charge state. Forthe samarium doped glass heat treated at 250 C (<Tg) the Sm2+ luminescence was also observed. Theanalysis of the luminescence efficiency was performed in the interval range of 14 K to room temperature,where the integrated intensity of the luminescence was found to decrease for the Sm3+ and Tb3+ ions inthe studied temperature range. Luminescence decay curves were found to be non-exponential for the4G5/2?6H7/2 and 5D3?7F4 transitions of the Sm3+ and Tb3+ ions, respectively. The results strongly suggestthe occurrence of energy transfer processes through cross relaxation phenomena, mediated by dipole-dipoleinteraction in all the studied samples. The decay of the 5D4?7F5 emission of the Tb3+ ions was found to besingle exponential with a time constant of 3.1ms. Based on the spectroscopic characteristics, models forrecombination processes are proposed. The room temperature luminance photometric properties with ultravioletexcitation show that the samarium doped glasses have much lower luminance intensity (around0.3 Cd/m2) when compared with the 6-7Cd/m2 observed for the terbium doped ones.