Glassy materials are promising intercalation compounds, due to their open network structure and absence of grain boundaries. Some glasses containing alkali ions and a high concentration of transition metal ions can present mixed ionic-electronic conductivity and are therefore potential candidates for application as cathode material in Li-ion batteries. The present work is devoted to the ternary system xLi(2)O-(1-x)[0.3V(2)O(5)-0.7TeO(2)] with 0 <= x <= 0.4. These compounds were prepared by heat treatment in air at 800 degrees C followed by traditional quenching. Raman spectroscopy and V-51 nuclear magnetic resonance measurements were performed in order to highlight the structural short range order modifications induced by the introduction of the Li2O network modifier. These structural effects can be related to the electrical behaviour, as studied by complex impedance spectroscopy measurements. (c) 2006 Elsevier B.V. All rights reserved.