(Pentamethylcyclopentadienyl)rhodium (RhCp*)‐catalyzed CH transformations have emerged as a prosperous field in CH bond activation. Recent advances in this area have significantly focused on the development of new strategies for CC and Cheteroatom bond formation that are characterized by the novel reactivity of the RhCp* catalyst to undergo formal SN‐type reactions with electrophilic substrates. This review is intended to give an overview on this rather new class of RhCp*‐catalyzed CH transformations, covering recent CC and Cheteroatom bond‐forming reactions. The nature of the reaction partner in these CH functionalization reactions serves as a guideline throughout this article and, combined with selected descriptions of mechanistic proposals, should emphasize general characteristics of transformations within this novel reaction class.