Soft nucleophilic phosphinocatalysis has been known since the 1960s as a result of the pioneering work of Horner, Price, Rauhut−Currier, and Morita. In the 1990s, Trost and Lu made important discoveries, reporting isomerization, umpolung addition, and [3+2] cycloaddition. Nonetheless, it was not until the 2000s that the area of phosphinocatalysis began to flourish. My group, through careful analysis of the mechanism of the phosphinocatalysis reactions, has demonstrated over two dozen new reactions facilitated by phosphine catalysts. The results are a one‐step conversion of simple acyclic starting materials into various carbo‐ and heterocycles. The practical values of these one‐step phosphine‐catalyzed annulation processes are significant since (1) they are atom‐economic and environmentally friendly, and (2) the heterocycles are an immense class of organic compounds with numerous practical applications. One recent, particularly significant advancement is the creation of chiral phosphines that are derived from a natural amino acid, hydroxyproline. Their synthetic utility in the phosphine‐catalyzed annulations, application in total syntheses of (+)-ibophyllidine and (–)-actinophyllic acid, and commercialization will also be discussed.