The underpotential deposition (UPD) of Ag on an iodine-coated Au(111) surface has been examined in perchloric acid solution by electrochemical scanning tunneling microscopy (STM). A (5 x square-root 3) structure for the iodine adlayer was observed over wide terraces before initiating the UPD of Ag. Two different structures of (3 x 3) were found for the first UPD layer of Ag. It was expected by STM measurements that the iodine exchanges and exists above the layer of bulk deposited Ag. The structure of iodine on bulk deposited Ag is a simple (square-root 3 x 3 square-root)R30-degrees with no regularly arrayed phase boundaries.