Asymmetric organocatalytic oxidations have been witnessed to an impressive development in the last years thanks to the establishment of important chiral hypervalent iodines(III/V). Many different approaches involving both stoichiometric and catalytic versions have provided a fundamental advance in this area within asymmetric synthesis. The easily handing, nontoxic, mild, environmentally friendly (green oxidants), and high stability that are features of these reagents have been applied to many reactions and also have allowed exploring further unprecedented enantioselective transformations. The intention of the present review is thus to highlight as a whole the many approaches utilized up to date to prepare chiral iodines(III/V), as well as their reactivity in a comprehensive manner.