The glass samples of composition 60V 2 O 5 À5P 2 O 5 À(35 ¡ x) B 2 O 3 ÀxCeO 2 , (0 x 5) containing rare earth CeO 2 were prepared by the conventional melt-quenching method. The samples were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy and thermo gravimetricÀdifferential thermal analysis (TG-DTA). The glass transition temperature and crystallization temperature were determined from the TG-DTA analysis. The activation energy for endo and exo was evaluated. The DC electrical conductivity has been carried out in the temperature range 303À473 K. The maximum conductivity and minimum activation energy were found to be 0.039 S cm ¡1 and 0.15 eV, respectively, at 473 K for x D 1. The ionic conductivity was found to be dominant over the electronic conductivity and varies between 86% and 95%. The change in density and molar volume were discussed in terms of structural modification.