A new glassy solid electrolyte system C(x)Ag(1-x)l-Ag2O-V2O5 has been synthesized. The structural, thermal and electrical properties of the samples have been investigated. The glassy nature of the samples is confirmed by XRay diffraction and Differential Scanning Calorimetry studies. The electrical conductivity of these samples increases with Cul content and approaches a maximum value of similar to 10(-2) Omega(-1) cm-(1) for x = 0.35 at room temperature. Ionic mobility measurements suggest that enhancement in the conductivity With Cu+ ion substitution may be attributed to increase in the mobility of Ag+ ions. The electrical conductivity versus temperature cycles carried out at well-controlled heating rate above T-g and T-c reveal interesting thermal properties. For lower Cul content samples conductivity exhibits anomalous rise above T-g and subsequent fall at T-c It is also found that Cul addition into Agl-Ag2O-V2O5 matrix reduces the extent of crystallization. (C) 2009 Elsevier B.V. All rights reserved.