A series of novel Er3+-doped bismuth-germanate glasses containing different tungsten concentrations with a molar composition of 97.5[(75 − x)GeO2–25Bi2O3–(x)WO3]–2Sb2O3–0.5Er2O3(x = 5, 10, 15, 20, and 25 mol%) were fabricated. Their thermal properties are measured by differential scanning calorimetry. A structural investigation by Raman spectroscopy suggested that changes occurred in the glass network by WO3incorporation. By laser excitation at 980 nm, a strong emission from Er3+ions at 1532 nm is observed, while the WO3addition caused changes in the emission spectra. The emission cross-section spectra of Er3+are calculated by both McCumber and Füchtbauer–Ladenburg theories and their comparison showed these theories yielded slightly different results, but in both cases, the calculations showed that a gain signal in L-band can be achieved when 30% of the Er3+ions are at the excited state. This study proves that the Er3+-doped bismuth-germanate glasses are suitable for optical fiber amplifier applications operating at C- and L-band.