The hydration of halogens has been widely researched because of its close relation with the water desalination and biochemical reactions. In this work, by a combination of scanning tunneling microscopy and X-ray photoelectron spectroscopy, we have explored the hydration process of iodine via the Eley-Rideal process on the Au(111) surface. Moreover, the hydration process of iodine with the presence of the NiPc self-assembled network as a template has also been investigated, where the stepwise hydration of iodine at room temperature can be visualized on Au(111).