Dedicated to the memory of Prof. José Barluenga The unique reactivity of diaryliodonium salts with copper complexes has been applied to a variety of synthetic organic transformations. These hypervalent iodine compounds have been used for diverse copper-catalyzed cross-coupling reactions including C–H functionalizations, enantioselective C–C bond formation, cascade reactions and different heteroatom arylation processes. This review provides a summary of recent developments on this topic and discusses both the synthetic utility and mechanisms of these transformations. 1 Introduction 2 Historical Background 3 Arylation of Carbon Nucleophiles 3.1 Arylation of Organometallic Compounds 3.2 Arylation of Heteroarenes 3.3 Arylation of Arenes 3.4 Arylation of Alkenes 3.5 Arylation of Alkynes 4 Nitrogen Arylation 4.1 Arylation of Acyclic Amine Derivatives 4.2 Arylation of Cyclic Amine Derivatives 4.3 Arylation of Nitriles 4.4 Arylation of Azides 5 Oxygen Arylation 6 Arylation of Other Heteroatoms 6.1 Fluorine Arylation 6.2 Sulfur Arylation 6.3 Phosphorus Arylation 6.4 Iodine Arylation 7 Summary and Conclusions