(AgI)(x)(As2Se3)(1-x) glass powders were successfully obtained up to 70 mol% AgI content by the mechanical milling method. Electrical conductivities, which show the exponential increase with addition of AgI, are comparable to the values of the corresponding melt-quenched glasses. The conductivity of 60 mol% AgI-doped glass shows great increase at the early period of the milling. A DSC signal for the beta-alpha phases transition of crystalline AgI becomes weak at the medium stage of the milling, whereas glass transition appears clearly. EXAFS measurements at Ag, I, As, and Se K-edges have been carried out for (AgI)(0.6)(As2Se3)(0.4) glasses with different period of the milling. The amorphization process of (AgI)(0.6)(As2Se3)(0.4) system was accompanied by a decrease of the nearest neighboring coordination number of Ag at the medium stage of the milling. These results suggest that the structural disordering of AgI units in the glass matrix would be strongly related to the appearance of fast ionic conduction. (c) 2007 Elsevier B.V. All rights reserved.