Electronically conducting glasses of the composition xV(2)O(5)(.)(100-x)P2O5 for 60 < x < 90 were prepared. The glasses of the composition corresponding to x=90 exhibited the highest electrical conductivity and they-were studied in more detail. The effects of the annealing of the samples on their electrical conductivity, structure and other characteristics were studied by impedance spectroscopy, X-ray diffractometry, DSC and SEM microscopy. It was shown that, at temperatures close to the crystallization temperature T, (determined from DSC), these glasses turned into nanomaterials consisting of crystalline grains Of V2O5 (average size 25-35 mn) embedded in the glassy matrix. Their electrical conductivity was higher and the temperature stability was better than those of the starting glasses. It is postulated that the major role in this conductivity enhancement is played by the interfacial regions between crystalline and amorphous phases. The annealing at temperatures exceeding T, led to massive crystallization and to a conductivity drop. The XRD and SEM observations have shown that the material under study undergoes structural changes: from amorphous at the beginning, to partly crystalline after the annealing at 340 degrees C and to polycrystalline after the annealing at 530 degrees C. The obtained results are in agreement with those of our earlier studies on mixed electronic-ionic conducting glasses of the ternary Li2OV2O5-P2O5 System. (c) 2006 Published by Elsevier B.V.