Palladium compounds containing a Pd‐C that are stabilized intramolecularly by at least one two‐electron donor group have numerous applications as pre‐catalysts. In particular, these compounds denominated palladacycles possess very attractive properties such as high thermal stability and low air sensitivity and they are ease to handle. These compounds are very active catalyst precursors in Heck coupling, Suzuki coupling, Buchwald–Hartwig amination and related coupling reactions under mild conditions, for instance at room temperature or in water. However, palladacycles serve as precursors to highly active palladium(0) species consist of soluble clusters or colloids, often stabilized by quaternary ammonium salts in highly dilute solutions or highly active low‐coordinate complexes of electron‐rich phosphines or carbenes. Moreover, chiral palladacycles are very important catalysts for enantioselective allylic rearrangements, allylic additions and aldol chemistry, since they act as Pd(II) Lewis acids and no redox process occurs