The enhanced stabilization of a carbocationic site adjacent to a ferrocenyl moiety was recognized within a few years of the discovery of sandwich compounds. While a detailed understanding of the phenomenon was the subject of some early debate, researchers soon took advantage of it to control the ease and direction of a wide range of molecular rearrangements. We, here, discuss the progress in this area from the pioneering studies of the 1960s, to more recent applications in chromatography and analytical detection techniques, and currently in the realm of bioactive organometallic complexes. Several classic reactions involving ferrocenyl migrations, such as the pinacol, Wolff, Beckmann, and Curtius, are discussed, as well as the influence of the ferrocenyl substituent on the mechanisms of the Nazarov, Meyer-Schuster, benzoin, and Stevens rearrangements. The preparation and isomerizations of ferrocenyl-stabilized vinyl cations and vinylcyclopropenes, together with the specific cyclization of acetylcyclopentadienyl-metal derivatives to form 1,3,5-substituted benzenes, demonstrate the versatility and generality of this approach.