Effect of Cu2O substitution in 50AgI-33.33[(Cu2O)(x), (Ag2O)(1-x)]-16.67V(2)O(5) glass matrix is discussed. Glassy nature of the samples is confirmed by differential scanning calorimetry and X-ray diffraction. The electrical conductivity of these samples is found to be increasing with Cu2O content and approaches a maximum value of similar to 2 x 10(-2) Omega(-1) cm(-1) for x = 03 at room temperature. Ionic mobility, measured using transient ionic current technique, increases with Cu2O content significantly. These samples are found to be predominantly Ag+ ion conducting in nature. High Cu2O content samples (x >= 0.3) though exhibit nanocomposite nature as revealed by scanning electron microscopy, the conductivity enhancement is found to be due to compositional changes that eventually lead to ionic mobility rise. (C) 2012 Elsevier B.V. All rights reserved.