Vanadium pentoxide glassy-crystalline nanostructured materials were prepared by solidification of the molten V2O5, using the twin rollers technique. The studied materials were characterized by: X-ray diffractometry (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and impedance spectroscopy (IS). It was found that the morphology, the relative content of the glassy and crystalline phases, and the average dimensions of the V2O5 nanocrystallites in the glassy matrix depended on the synthesis parameters (temperature and duration of melting, twin rollers speed, additional grinding). The pelletized samples exhibited considerable electrical conductivity of ca. 10(-3) Scm(-1) at room temperature. Preliminary charge-discharge tests of laboratory lithium metal batteries with cathodes based on the materials under study have been carried out. (C) 2011 Elsevier B.V. All rights reserved.