Most of iodine was captured by the block when NaI solution flowed through a bentonite block sorbed silver to retard the migration of iodine released from high-level radioactive wastes. In order to understand in detail the mechanism for the retardation of the iodine by the silver ion, X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectra of the silver sorbed bentonite before and after the contact with iodide were compared with those of AgO, $Ag_2O$ and AgI as references. This examination suggests that the silver ion sorbed on the bentonite is desorbed, and then it retards the migration of iodine by forming the cluster of AgI precipitate.