The Sm3+/Gd3+ co-doped glasses in the B2O3–GeO2–PbO and B2O3–GeO2–Bi2O3 systems have been synthesized in the composition range of 40B2O3–40GeO2–(15-17)PbO(Bi2O3)–(3-2)Sm2O3–(2-1)Gd2O3 and 42.5B2O3–42.5GeO2–(11.25-12.75)PbO(Bi2O3)–(2.25-1.5)Sm2O3–(1.5-0.075)Gd2O3. The physical, structural, and spectral properties of the produced glasses have been studied. The fabricated glass samples demonstrated changes in temperature-sensitive luminescence parameters in 298-673 K temperature range. We found out several photoluminescence bands attributed with transitions from different Stark sublevels. By using a combination of two temperature sensitive and one non-sensitive transitions we calculated fluorescence intensities ratio (FIR). This procedure made it possible to increase the sensitivity of luminescence thermometry in several times. Such method could be very useful for the luminescent thermometry materials based on Ln3+ ions with multiplied f-f transitions.