Selective functionalization of ubiquitous CÀ H bonds of molecules would provide novel retrosynthetic insights and powerful tools for the rapid construction of molecular complexity. In this context, Cp*Ir(III) complexes have exhibited versatile reactivity towards the selective conversion of CÀ H bonds, with key features that include the use of readily transformable raw materials, great selectivity (chemo-, stereo-and regio-), high efficiency, mild reaction conditions and they enable late-stage modification of complex molecules. Recently, Cp*Ir(III) catalysis has achieved a broad range of reactions such as multiple dehydrogenations and stereoselective CÀ X bond formations. These advancements are valuable to organometallic chemists and enable the efficient synthesis of functionalized architectures.