The chemistry of Polyvalent Iodine ranging from structure and bonding, preparation, compounds to the various computational and experimental structures was studied. The main purpose of this study is to summarize the data that appeared in the literature following publication of some previous reviews, and was organized according to the classes of organic polyvalent iodine compounds, by emphasizing their synthetic application. The number of X-ray crystal structures have also been reported for the main classes of organic polyvalent iodine compounds. Several compounds as Iodine (III) compounds, Iodosylarenes, and Fluorides and chlorides were also investigated. The Iodine (III)compound is exhibiting growing interests mainly due to their useful oxidizing properties, combined with their bening environmental character and commercial availability.