The structure of Ag2O-MxOy-TeO2 (MxOy = WO3, MoO3, P2O5, and B2O3) glasses was investigated by Raman spectroscopy. Raman spectra shows that in addition to the expected TeO4 trigonal bipyramid (tbp), the TeO3 trigonal pyramid (tp), and the WO4/WO6, MoO4/MoO6, PO4, and BO3/BO4 polyhedra are present in tungstotellurite, molybdotellurite, phosphotellurite, and borotellurite glasses, respectively. The relation between the MxOy content and the intensity ratios of the deconvoluted Raman peaks I-720/I-660 and I-780/I-660 were studied. From the temperature variation study of the Raman spectra, it was observed that there is an increase in the TeO3 units with the increasing temperature. Although crystallization occurred easily during heating of the glasses in any system, the melts hardly ever crystallized during cooling.