An intense broadband 1.53-μm emission with a full width at half-maximum of 51.2 nm and peak emission cross-section of 8.58×10-21 cm2 of Er3+-doped Ga2O3-GeO2-Bi2O3-R2O (R= Na+, K+) glass have been obtained upon 980 nm diode-laser excitation. Effects of alkali metal ions on the thermal stability and spectroscopic properties of Er3+-doped Ga2O3-GeO2-Bi2O3 glass have been investigated. It is found that the incorporation of Na+ replacing K+ into Er3+-doped Ga2O3-GeO2-Bi2O3 glass can effectively improve the 1.53-μm emission and deduce upconversion luminescence .The results show that Ga2O3-GeO2-Bi2O3-Na2O glass might be an attractive host material for their application in C-band optical fiber amplifiers.