This Minireview provides insight into the early history of nucleophilic phosphinocatalysis. The concepts of 1,4‐addition of a tertiary phosphine to an α,β‐enone and of equilibrium between the resulting phosphonium zwitterion and phosphonium ylide established a fundamental basis for the development of several classical transformations, including the Rauhut‐Currier, Morita, McClure‐Baizer‐Anderson, and Oda reactions.