TeO2 based glasses with molar composition (70−x−y)TeO2-20WO3-10Y2O3-xEr2O3-yYb2O3, where x=0 and 0.5mol% and y=0, 0.5, 1, 2 and 4mol%, were prepared by the melt quenching technique. At room temperature, all the samples are transparent, mechanical and thermally stable. This vitreous system was found to be promising for potential applications in optical amplification, in particular in erbium doped fiber amplifiers (EDFA), Raman optical amplifiers and also in spectral conversion for applications in photovoltaic technology.The Raman spectrum of the base glass (Er0Yb0), using laser excitation of 532nm, showed vibrational bands related to TeO and WO bonds. The introduction of WO3 results in a higher bandwidth relatively to SiO2 based glasses and even other TeO2 based glasses, making this vitreous system promising for Raman optical amplification.With regard to the optical analysis, an increase of the intensity of the upconversion emission with the increase of the content of the sensitizer ions Yb3+ was observed. The Er3+ emission around 1540nm has a full width at half maximum of about 100nm in the temperature range of 70–300K, which is a very interesting value relatively to those reported for other glassy systems, considering optical amplification as a potential application.