The chemistry of polyvalent iodine organic compounds has seen significant growth since the early 1990s, driven by their useful oxidizing properties, benign environmental impact, and commercial availability. This review covers the synthetic applications of various polyvalent iodine compounds, including 2-iodoxybenzoic acid (IBX) and similar iodine(V) derivatives, polymer-supported and recyclable polyvalent iodine reagents, catalytic applications, and structural studies of complexes and supramolecular assemblies. The main focus is on the classes of organic polyvalent iodine compounds, with emphasis on their synthetic applications. The review also discusses the structure and bonding of these compounds, computational studies, and experimental structural studies. Specific sections cover iodine(III) compounds, fluorides, chlorides, and [bis(acyloxy)iodo]arenes, detailing their preparation, structural characteristics, and synthetic applications.The chemistry of polyvalent iodine organic compounds has seen significant growth since the early 1990s, driven by their useful oxidizing properties, benign environmental impact, and commercial availability. This review covers the synthetic applications of various polyvalent iodine compounds, including 2-iodoxybenzoic acid (IBX) and similar iodine(V) derivatives, polymer-supported and recyclable polyvalent iodine reagents, catalytic applications, and structural studies of complexes and supramolecular assemblies. The main focus is on the classes of organic polyvalent iodine compounds, with emphasis on their synthetic applications. The review also discusses the structure and bonding of these compounds, computational studies, and experimental structural studies. Specific sections cover iodine(III) compounds, fluorides, chlorides, and [bis(acyloxy)iodo]arenes, detailing their preparation, structural characteristics, and synthetic applications.