The effects of P2O5 and Ga2O3 addition on Raman scattering and thermal stability characteristics of TeO2-BaO-SrO-Nb2O5 (TBSN) glasses were investigated. The results show that the relative Raman scattering cross section decreases, but the Raman gain bandwidth increases greatly with P2O5 addition increase. In TBSN-10Ga-P[(75-x)TeO2-5BaO-5SrO- 5Nb2O5 -10Ga2O3-xP2O5 (x = 0, 4, 8, 12, 16, 20)] and TBSN-16P-Ga series [(69-y)TeO2-5BaO-5SrO-5Nb2O5- 16P2O5-yGa2O3 (y = 0, 2, 4, 6, 8, 10)] glasses, the addition of Ga2O3 results in flatness of 350-1250 cm-1 band, but decrease in the relative Raman scattering cross section and Raman gain bandwidth. The Raman gain coefficients of the glasses were calculated. The results show that TBSN-4P has the largest gain coefficient (8.70 × 10-12 m/W), and TBSN-24P persists the widest bandwidth (621 cm-1), which is 45 times and 2.95 times of those for silica glass, respectively. The thermal stability against crystallization of TBSN glasses can be improved dramatically when doped with P2O5, but it gets worse with Ga2O3 and P2O5 co-doping.