A series of new Er3+/Yb3+-codoped 70TeO2-5Li2O-(25-x)B2O3-xGeO2 (TLBG, x = 0, 5, 10, 15, 20mol%)glasses are prepared. The thermal stability and spectroscopic properties of TLBG glasses are studied. It is found that these glasses have the better thermal stability ( ( Tx - Tg) ＞ 150℃) compared with 75 TeO2-20 ZnO-5Na2O (TZN) glass. The fluorescence full width at half maximum (FWHM) is about 77nm, while the emission intensity and the quantum efficiency of the 4I13/2 level of Er3+ increase with the increasing GeO2 content. The maximum quantum efficiency and stimulated emission cross-section of Er3+ calculated from the McCumber theory are 93.82% and 9.0 × 10-21 cm2, respectively. The products of FWHM and σepeak of Er3+ in TLBG glasses are larger than those in other reported glasses. The obtained data indicate that this kind of TLBG glasses is a promising candidate host material for Er3+-doped broadband amplifiers.