Silver aluminophosphate glasses have been investigated as matrices for the immobilization of radioactive iodine. In this study, up to 28 mol% AgI have been incorporated without volatilization thanks to a low temperature synthesis protocol. Alumina was added in the composition in order to increase the glass transition temperature for a better thermal stability in a repository conditions. Two series of glasses have been investigated, based on AgPO3 and Ag5P3O10 compositions, and with 0-5 mol% Al2O3. We report P-31, Al-27 and Ag-109 NMR study of these glasses, including advanced measurement of the connectivities through {Al-27}-P-31 cross-polarization and P-31-P-31 double-quantum correlation. We confirm that AgI is inserted in the aluminophosphate glasses and does not form clusters. AgI does not induce any modification of the glass polymerization but only an expansion of the network. Despite no evidence for crystallization could be obtained from XRD, NMR revealed that the introduction of AgI induces an exclusion of alumina from the network, leading to the crystallization of aluminophosphate phases such as Al(PO3)(3) or AlPO4. As a consequence, despite NMR gives evidence for the presence of aluminophosphate bonds, only a limited effect of alumina addition on thermal properties is observed. (C) 2013 Elsevier B.V. All rights reserved.