Ag2O-P2O5 and Ag2O-P2O5-20 wt% CdCl2 glasses were prepared by melt quenching method and characterized with the help of several experimental techniques. Powder X-ray diffraction study indicated that the glasses are amorphous in nature. DSC studies showed that CdCl2 doped glass is chemically more durable. Electrical conductivity and ionic transference number measurements have shown that both the glasses are ionic conductors with Ag+ ions as the charge carriers. The electrical conductivity of the doped glass is found to be higher than the undoped one. Structures of the glasses have been proposed on the basis of IR spectral analysis. From SEM studies it has been inferred that addition of 20 wt% CdCl2 modifies the morphology of Ag2O-P2O5 glass and in its presence fort-nation of clusters composed of nanofibers occur. (C) 2007 Elsevier Ltd. All rights reserved.