Glasses of the TeO2-WO3-Yb2O3 system are synthesized for wide range of Yb3+ concentrations of up to 6.0 × 1021 ions/cm3. The spectral-luminescent properties of lightly doped samples are investigated at room temperature and at the boiling point of liquid nitrogen. The energies of the Stark levels of the ground and excited states of Yb3+ ions incorporated into tungsten–tellurite glass are determined by analyzing the low-temperature spectra. The absorption, emission, and gain cross section spectra are obtained. The excess of the measured fluorescence decay time over the radiative lifetime ∼0.3 ms derived from the absorption spectra is attributed to the reabsorption effect in bulk samples. Measurements of lightly doped glass powder in the immersion liquid are made to reduce the effect of reabsorption. The fluorescence decay time of the powder is very close to the calculated radiative lifetime. Compared with phosphate, silicate, and other Yb3+-doped glasses, the tungsten–tellurite glass has a promising potential as a gain medium for lasers and amplifiers.