An optical spectroscopy analysis of TeO-GeO2-ZnO glass co-activating Sm3+/Tb3+ ions was carried out through Raman, photoluminescence spectra and decay time profiles as a function of Sm3+ concentration. According to the estimated CIE1931 chromaticity coordinates, the color of the emission can be adjusted from the yellow light region (0.4883, 0.4774), towards the reddish light region (0.5194,0.4144) by increasing the Sm3+ content from 1, 3, 5% mol, co-doped with 1% mol Tb3+ under co-excitation of Sm3+ and Tb3+ at 378 nm. The color temperatures are in the range of 1379–2804 K. Such photoluminescence is generated by the 4G 5/2 → 4H 5/2, 4H 7/2, 4H9/2 emissions of Sm3+ in addition to the 5D4→7F6,5,4,3 emissions of Tb3+; the single doped Sm3+ glass displayed an intense orange light. Meanwhile, co-doped Sm3+/Tb3+ glasses excited at 378 nm showed a significant reduction in Tb3+ emission, with a simultaneous increment in the reddish-orange emission of Sm3+, due to a non-radiative resonant energy transfer from Tb3+ to Sm3+. Decay time profile analysis of the Tb3+ emission as function of Sm3+ ion content suggests that an electric dipole–dipole interaction into Tb3+–Sm3+ clusters might dominate in the energy transfer process, with an efficiency and probability of 0.22, 0.27, 0.38 and 122.8, 327.6, 522.7 s−1, respectively.