The Raman spectroscopy technique was used to characterize the microstructure and the crystallization properties of the as-cast and heat-treated binary TeO2-WO3. TeO2-CdF2 and ternary TeO2-CdF2-WO3 glasses and glass ceramics. The results were compared with those obtained by using the X-ray diffraction technique. The effect of the WO3 and CdF2 contents on the TeO2 glass network and the intensity ratios of the deconvoluted Raman peaks were determined. The shifts in the Raman band wavenumbers and the intensity values for each band were investigated. The Raman results indicated that the glasses were mainly formed by the [TeO4] and [TeO3] units. The [Teal] units convert to [TeO3] units with the addition of WO3 and CdF2 into tellurite glasses. All the crystalline phases such as alpha-TeO2, delta-TeO2 and gamma-TeO2 existing in the TeO2-WO3, TeO2-CdF2 and TeO2-WO3. TeO2-CdF2 glasses were determined. The transformation of the metastable gamma-TeO2 phase into stable alpha-TeO2 was observed for the (1 x)TeO2 -xWO(3) (where x = 0.15, 0.20, 0.25), 0.90Te(2)-0.10CdF(2), the 0.85TeO(2)-0.10CdF(2)-0.05WO(3) and 0.80TeO(2)-CdF2-WO3 glasses, and the transformation of the metastable 3-o(2) phase into the stable alpha-TeO2 was also observed for the TeO2-CdF2-WO3 glass system. In addition, an unidentified phase formation, labeled e, was determined. Copyright (C) 2009 John Wiley & Sons, Ltd.