Glasses in the TeO2-WO3-Li2O system were prepared by using conventional melt-quenching technique. Glass formation range of the system and thermal, physical and structural features of the ternary glasses were investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and FTIR analysis according to the equimolar substitution of TeO2 by WO3 + Li2O and increasing Li2O content at constant TeO2. Thermal behavior of the glasses was studied in terms of glass transition temperature (T-g), crystallization temperature (T-c/T-p) and glass stability against crystallization (Delta T). Density (rho), molar volume (V-M), oxygen molar volume (V-o), oxygen packing density (OPD), average cross-link density ((n) over bar (c))Poisson's ratio (mu(cal)) and number of bonds per unit volume (n(b)) values were calculated for the physical investigation of the glasses. FTIR spectra of the glasses were interpreted in terms of the structural transformations on the glass network by the changing composition. (C) 2013 Elsevier B.V. All rights reserved.